DE102011089060A1 - Use of an active ingredient combination comprising a water-soluble polymer including a group, and a polar alkoxysilane compound for improving artificial colors of coloring compounds on keratin fibers, preferably human hair - Google Patents

Abstract

Use of an active ingredient combination comprising (a) at least one water-soluble polymer comprising at least one group of (I), and (b) at least one polar alkoxysilane compound of (II) for improving artificial colors of coloring compounds on keratin fibers, preferably human hair, is claimed. Use of an active ingredient combination comprising (a) at least one water-soluble polymer comprising at least one group of formula (-Si(OR) x(R1) 3 - x) (I), and (b) at least one polar alkoxysilane compound of formula (((R2) 3 - x(RO) x) (Si-G-K2-R1)) (II) for improving artificial colors of coloring compounds on keratin fibers, preferably human hair, is claimed. R, R1 : 1-4C alkyl, preferably methyl or ethyl; x : 1, 2 or 3; G : 1-3C alkylene; K2 : connectivity, preferably covalent bond or molecule fragment with two free valencies; and R2 : molecular fragment with at least one polar substituents, preferably at least one quaternary N, amino or anionic group. . An independent claim is also included for a cosmetic agent for dyeing keratin containing fibers, preferably human hair, comprising the above mentioned active ingredient combination and (c) at least one color-producing compound in a cosmetic carrier.

Description

The present invention relates to cosmetic agents for coloring keratin-containing fibers.

For the provision of cosmetic agents for dyeing, in particular for keratin-containing fibers such as, for example, human hair, the person skilled in the art knows various dyeing systems depending on the requirements of the dyeing.

For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes. The oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings but usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading.

The developer components used are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, heterocyclic hydrazones, diaminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives. As coupler components m-phenylenediamine derivatives, naphthols, pyridine derivatives, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used.

For temporary dyeings usually dyeing or tinting agents are used, which contain as dyeing component so-called rectifying dyes. These are dye molecules that attach directly to the substrate and do not require an oxidative process to form the paint. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more rapid undesirable change in shade or even a visible, homogeneous color loss occurs much faster.

Finally, another dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the substrate, e.g. As hair applied; These then form naturally-analogous dyes in the course of oxidative processes in the hair. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The dyeing can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agent must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. On the other hand, satisfactory results can often only be achieved for use in persons with originally red and, in particular, dark to black hair color, by using other dye components, in particular special oxidation dye precursors.

An improvement, for example, the color intensity or the tinting strength of the dyes used has z. As a result, that expensive dyes can be used more economically. The dyeings obtained should continue to a high degree of color fastness z. B. against sweat, washing, light or friction and must be compatible with the use of other hair treatment products, especially in the context of hair care. Uniform coloring along the keratin-containing fibers is also a requirement for a commercially successful keratinous fiber colorant. Keratinic fibers, particularly human hair, are unevenly grown natural products in their structural nature along the fiber. The keratinous material of the fiber in the hair lengths and the hair tips, for example, has been exposed to environmental influences over a longer period of time than the regions of the fiber near the hair root and therefore show greater changes in the originally grown fiber structure. Differences in the fiber structure often lead to uneven ink absorption and to uneven wear of the dyeing by environmental influences. The coloration is visually perceived as uneven.

It was therefore an object of the present invention to provide a cosmetic composition which dyes the keratin-containing fibers and which produces an improved coloration and does not have the abovementioned disadvantages.

In the publication WO-A1-2009 / 024450 describes star-shaped polyether-containing compounds which find use in agents for cleaning surfaces and restrain re-soiling of the purified substrate.

In the pamphlets WO-A1-2011 / 015512 . WO-A1-201 1/01 5513 and WO-A1-2011 / 015514 alkoxysilylated, polyether-containing compounds are proposed for use on the hair.

The improvement of the color fastness of artificial dyeings on keratin-containing fibers by alkoxysilylated, polyether-containing compounds is not known from the prior art.

• (a) mindestens einem wasserlöslichen Polymer umfassend mindestens einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, und
• (b) mindestens einer polaren Alkoxysilanverbindung der Formel (SI)
  
  worin G für eine (C₁ bis C₃)-Alkylengruppe steht, K'' für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen steht, R¹ für ein Molekülfragment steht, umfassend mindestens einen polaren Substituenten ausgewählt aus mindestens einem Vertreter aus der Gruppe, die gebildet wird aus quaternisierten Stickstoffatomen Aminogruppen anionischen Resten x für 1, 2 oder 3 steht, R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen,

zur Verbesserung künstlicher Färbungen farbgebender Verbindungen auf keratinhaltigen Fasern, insbesondere menschlichen Haaren.A first object is therefore the use of a drug combination of

• (A) at least one water-soluble polymer comprising at least one radical * -Si (OR) _x (R ') _3-x , wherein R and R' independently of one another for a (C ₁ to C ₄ ) alkyl group (in particular methyl or ethyl ), x is 1, 2 or 3, and
• (b) at least one polar alkoxysilane compound of the formula (SI)
  
  wherein G is a (C ₁ to C ₃ ) alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized nitrogen atoms, amino groups of anionic radicals x is 1, 2 or 3, R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) stand,

for improving artificial colorations of coloring compounds on keratin-containing fibers, in particular human hair.

It turned out that the use of said active substance combination on already dyed keratin-containing fiber (in particular during the dyeing process) improves the color fastness of the dyeing, in particular the wash fastness of the dyeing. By repeated washing of the fiber is formed along the keratin fiber from the approach to the tips no uneven coloration by uneven washing out of the paint. The coloring retains its good leveling.

According to the invention, keratin-containing fibers are understood to mean furs, wool, feathers and, in particular, human hair.

• (1) aus mindestens einem Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusätzlich mindestens einer Kupplerkomponente und/oder
• (2) aus mindestens einem direktziehenden Farbstoff und/oder
• (3) aus mindestens einer Vorstufe naturanaloger Farbstoffe.

The coloring compounds according to the present invention are preferably selected

• (1) at least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or
• (2) from at least one direct dye and / or
• (3) from at least one precursor of naturally-colored dyes.

Particularly preferred coloring compounds are selected from at least one oxidation dye precursor of the developer component type and optionally additionally at least one coupler component.

Preferred representatives of the coloring compounds of (1), (2) and (3) (vide supra) are defined in the second subject of the invention (vide infra).

Preferred representatives of the components (a) and (b) of said active ingredient combination (vide supra) are defined in the second subject of the invention (vide infra).

The cosmetic use of the present invention is improved by incorporating said drug combination into a cosmetic carrier. The following named cosmetic agents for coloring keratin fibers of the second subject of the invention are therefore preferably used.

• (a) mindestens ein wasserlösliches Polymer umfassend mindestens einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, und
• (b) mindestens eine polare Alkoxysilanverbindung der Formel (SI)
  
  worin G für eine (C₁ bis C₃)-Alkylengruppe steht, K'' für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen steht, R¹ für ein Molekülfragment steht, umfassend mindestens einen polaren Substituenten ausgewählt aus mindestens einem Vertreter aus der Gruppe, die gebildet wird aus quaternisierten Stickstoffatomen Aminogruppen anionischen Resten x für 1, 2 oder 3 steht, R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, und
• (c) mindestens eine farbgebende Verbindung.

A second object of the invention is therefore a cosmetic agent for coloring keratin-containing fibers, in particular human hair, contained in a cosmetic carrier

• (A) at least one water-soluble polymer comprising at least one radical * -Si (OR) _x (R ') _3-x , wherein R and R' independently of one another for a (C ₁ to C ₄ ) alkyl group (in particular methyl or ethyl ), x is 1, 2 or 3, and
• (b) at least one polar alkoxysilane compound of the formula (SI)
  
  wherein G is a (C ₁ to C ₃ ) alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized nitrogen atoms, amino groups of anionic radicals x is 1, 2 or 3, R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) stand, and
• (c) at least one coloring compound.

Preferred cosmetic carriers are water-containing cosmetic carriers, alcoholic cosmetic carriers or aqueous-alcoholic cosmetic carriers. For the purpose of coloring keratin-containing fibers, such carriers are, for example, lotions, water-in-oil emulsions, oil-in-water emulsions, creams, gels, foams or other preparations which are suitable for use on the hair.

For the purposes of the present invention, aqueous-alcoholic carriers are aqueous compositions containing 3 to 70% by weight of an organic solvent, in particular a C ₁ -C ₇ -alcohol (preferably ethanol, isopropanol, glycerol, benzyl alcohol, ethyldiglycol, 1,2-propylene glycol or 1,3-propylene glycol, methoxybutanol,). Preference is given to all water-soluble organic solvents.

The polar alkoxysilane compounds of component (b) are different from said water-soluble polymers of components (a).

If a chemical bond is marked with the symbol * in a representation of a structural formula, this represents a free valence of the corresponding structural fragment.

According to the invention, polymers are understood as meaning chemical compounds which have a molecular weight of at least 5000 g / mol. The polymers are composed of a plurality of molecules in which one or more kinds of atoms or atomic groupings (so-called constitutive units, basic building blocks or repeating units) are repeatedly arranged in a row. The polymers are obtained by polyreaction, the latter being synthetic (i.e., synthetic) or natural.

For the purposes of the present application, "water-soluble" are chemical compounds (eg polymers) if the chemical compound dissolves at pH 8 at 20 ° C. to more than 0.5 g in 100 g of water.

Substituents from the group which is formed from quaternized nitrogen atoms, amino groups, anionic radicals are polar in the sense of the application.

The said water-soluble polymers are preferably present in the compositions according to the invention in an amount of from 0.01 to 15.0% by weight, particularly preferably from 0.1 to 8.0% by weight, very particularly preferably from 0.2 to 5 , 0 wt .-%, most preferably from 0.25 to 2.5 wt .-%, each based on the weight of the total composition.

It is also preferred according to the invention, said water-soluble polymers of component (a) and the polar alkoxysilanes of component (b) in the compositions according to the invention in a weight ratio range of 10: 1 to 1: 10, preferably 4: 1 to 1: 4, particularly preferably from 1 to 1 to 1 to 2 to use.

• (i) eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten umfasst, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht der Polyoxyalkylenkette, und
• (ii) mindestens einen Rest *-Si(OR)_x(R')_3-x aufweist, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht.

As the preferred said water-soluble polymer is at least one water-soluble, polyether-modified, organic polymer having at least one polyether structural unit, said polyether structural unit

• (i) a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units comprising, with a maximum proportion of 50 wt .-% of propylene oxide units, based on the weight of the polyoxyalkylene chain, and
• (ii) at least one radical * -Si (OR) _x (R ') _3-x , wherein R and R' independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl), x stands for 1, 2 or 3.

By "polyether structural unit" is meant a chemical structure fragment comprising a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum of 50% by weight of propylene oxide units, based on the weight of the polyoxyalkylene chain. The polyether structural unit is optionally covalently bound directly or optionally via a chemical bond of a mediating structural fragment to a scaffold molecule. In this case, organic compounds or inorganic metal oxides are preferably used as the framework molecules. The former form a polyether-modified organic compound with the polyether moiety / polyether moieties. The latter form a polyether-modified solid particles with the polyether moiety / the Polyetherstruktureinheiten. By "organic compounds" is meant chemical compounds based on a hydrocarbon structural fragment. Corresponding hydrocarbon structural fragments are derived from linear, branched, cyclic or heterocyclic hydrocarbons, all of which may be saturated, unsaturated or aromatic.

According to the invention, "polyether-modified organic compounds" are understood as meaning organic compounds which have been modified with at least one polyether structural unit, the polyether structural unit each forming a chemical bond to the organic compound to be modified.

By "solid particles" is meant all particulate solids present at room temperature.

The term "polyether-modified solid particles" is understood according to the invention to mean solid particles which are surface-modified with polyethers, the polyethers comprising a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide Units based on the weight of the polyoxyalkylene chain.

In the context of the present invention, an ethylene oxide unit is a unit of the general formula (1) * -CH ₂ -CH ₂ -O- * Formula (1) and for the purposes of the present invention, a unit of the general formula (2) is understood to mean a propylene oxide unit. * -CH ₂ -CH (CH ₃ ) -O- * Formula (2) to understand.

If the polyoxyalkylene chain of the polyether structural unit contains ethylene oxide and propylene oxide units, the maximum proportion of propylene oxide units is preferably 40% by weight and particularly preferably not more than 30% by weight, based on the weight of the polyoxyalkylene chain.

• (i) eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten umfassen, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht der Polyoxyalkylenkette, und
• (ii) mindestens einen Rest *-Si(OR)_x(R')_3-x aufweisen, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht.

Within the scope of a particularly preferred embodiment, the water-soluble, polyether-modified, organic polymer having at least one polyether structural unit is selected from one or more polyether-modified, organic compounds which have at least three polyether structural units, this polyether structural unit

• (i) a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units comprising, with a maximum proportion of 50 wt .-% of propylene oxide units, based on the weight of the polyoxyalkylene chain, and
• (ii) have at least one radical * -Si (OR) _x (R ') _3-x , wherein R and R' independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl), x stands for 1, 2 or 3.

The polyether-modified, organic compounds are in the inventive compositions preferably in an amount of 0.01 to 15.0 wt .-%, particularly preferably from 0.1 to 8.0 wt .-%, most preferably 0.2 to 5.0 wt .-%, most preferably from 0.25 to 2.5 wt .-%, each based on the weight of the total composition.

Said water-soluble, polyether-modified, organic compounds are preferably selected from at least one compound of the general formula (PE-1) [Q ] ( K'-AKT) _n (PE-1) wherein
A denotes a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A,
K and K 'independently represent a connectivity selected from a covalent bond or from a molecular fragment having two free valences,
T stands for a rest * -Si (OR) _x (R ') _3-x , wherein R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl), x is 1, 2 or 3,
Q is an organic structural fragment derived from linear, branched, cyclic or heterocyclic hydrocarbons, all of which may be saturated, unsaturated or aromatic,
n stands for an integer from 3 to 64 (in particular for 3, 4, 5, 6, 7 or 8).

A is according to formula (PE-1) preferably a structural fragment of the formula (A1) * - (OCH ₂ CH ₂ ) _p - (OCH ₂ CH (CH ₃ )) _m - * (A1) wherein
p is an integer from 1 to 500,
m is an integer from 0 to 500 and
the structural fragment of the formula (A1) has a maximum proportion of 50% by weight of propylene oxide units, based on the weight of the structural fragment (A1). The ethylene oxide and propylene oxide units of the formula (PE-1) or of the formula (A1) may be randomly distributed or distributed in a gradient or present in at least two blocks.

If the group A of the compounds of the formula (PE-1) (or of all subsequent formulas containing the group A) is a polyoxyalkylene chain of ethylene oxide and propylene oxide units, the maximum proportion of propylene oxide units is preferably 40% by weight. and most preferably at most 30% by weight, based on the weight of A.

worin
R und R'' unabhängig voneinander stehen für Methylen, Ethan-1,2-diyl, Propan-1,2-diyl, Propan-1,3-diyl, Butan-1,2-diyl, Butan-1,3-diyl, Butan-1,4-diyl oder Phenylen,
R' ein Wasserstoffatom oder eine (C₁ bis C₄)-Alkylgruppe bedeutet,
R'' unabhängig voneinander eine (C₁ bis C₄)-Alkylgruppe oder eine Arylgruppe bedeutet.The radicals K and K 'according to formula (PE-1) are preferably, independently of one another, a covalent bond, an oxy group, a (C ₁ to C ₆ ) -alkylene group, an imino group or at least one of the following connectivities (K1) to (K10 )

wherein
R and R "independently represent methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl Butane-1,4-diyl or phenylene,
R 'represents a hydrogen atom or a (C ₁ to C ₄ ) -alkyl group,
R '' independently of one another is a (C ₁ to C ₄ ) -alkyl group or an aryl group.

T according to formula (PE-1) is preferably a radical * -Si (OR) _x (R ') _3-x , in which R and R' independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) and x is 2 or 3 (preferably triethoxysilyl).

Most preferably, the structural fragment -KT according to formulas (PE-1) stands for a group

The radical Q of the formula (PE-1) preferably represents an organic structural fragment having 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms. Q is preferably derived from glycerin, monosaccharide, disaccharide. Most preferably, Q is derived from a compound selected from sorbitol, 1,5-anhydro-sorbitol, 1,4-anhydrosorbitol, inositol, xylitol, mannitol, gluconolactone, glucuronic acid, 1,2,6-hexanetriol, hydroxyethylsorbitol, phytantriol , Hydroxypropyl phytantriol, lactitol, maltitol, pentaerythritol, polyglycerol-3, glucose, fructose, galactose, ribose, xylose, mannose, sucrose, cellobiose, gentiobiose, isomaltose, lactose, lactulose, maltose, maltutose, melibiose, trehalose, nigerose, palatinose, rutinose , Arabinose.

worin
mindestens drei Gruppen R für eine Gruppe *-(CH₂CH₂O)_p-(CHCH₃CH₂O)_m-K-T stehen und die übrigen Gruppen R für ein Wasserstoffatom oder eine Gruppe *-K-T stehen, worin unabhängig voneinander
p eine ganze Zahl von 1 bis 500 bedeutet und m eine ganze Zahl von 0 bis 500 bedeutet und p und m ein Verhältnis zueinander aufweisen, dass ein maximaler Anteil von 50 Gew.-% (bevorzugt maximal 40 Gew.-%, besonders bevorzugt maximal 30 Gew.-%) an Propylenoxid-Einheiten, bezogen auf das Gewicht der entsprechenden Polyoxyalkylenkette, vorliegt,
K steht für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen,
T steht für ein Molekülfragment umfassend mindestens einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht;

worin
mindestens drei Gruppen R für eine Gruppe *-(CH₂CH₂O)_p-(CHCH₃CH₂O)_m-K-T stehen und die übrigen Gruppen R für ein Wasserstoffatom oder eine Gruppe *-K-T stehen, worin unabhängig voneinander
p eine ganze Zahl von 1 bis 500 bedeutet und m eine ganze Zahl von 0 bis 500 bedeutet und p und m ein Verhältnis zueinander aufweisen, dass ein maximaler Anteil von 50 Gew.-% (bevorzugt maximal 40 Gew.-%, besonders bevorzugt maximal 30 Gew.-%) an Propylenoxid-Einheiten, bezogen auf das Gewicht der entsprechenden Polyoxyalkylenkette, vorliegt,
K steht für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen,
T steht für ein Molekülfragment umfassend mindestens einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht;

worin
mindestens drei Gruppen R für eine Gruppe *-(CH₂CH₂O)_p-(CHCH₃CH₂O)_m-K-T stehen und die übrigen Gruppen R für ein Wasserstoffatom oder eine Gruppe *-K-T stehen, worin unabhängig voneinander
p eine ganze Zahl von 1 bis 500 bedeutet und m eine ganze Zahl von 0 bis 500 bedeutet und p und m ein Verhältnis zueinander aufweisen, dass ein maximaler Anteil von 50 Gew.-% (bevorzugt maximal 40 Gew.-%, besonders bevorzugt maximal 30 Gew.-%) an Propylenoxid-Einheiten, bezogen auf das Gewicht der entsprechenden Polyoxyalkylenkette, vorliegt,
K steht für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen,
T steht für ein Molekülfragment umfassend mindestens einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht;

worin
mindestens drei Gruppen R für eine Gruppe -(CH₂CH₂O)_p-(CHCH₃CH₂O)_m-K-T stehen und die übrigen Gruppen R für ein Wasserstoffatom oder eine Gruppe -K-T stehen, worin unabhängig voneinander
p eine ganze Zahl von 1 bis 500 bedeutet und m eine ganze Zahl von 0 bis 500 bedeutet und p und m ein Verhältnis zueinander aufweisen, dass ein maximaler Anteil von 50 Gew.-% (bevorzugt maximal 40 Gew.-%, besonders bevorzugt maximal 30 Gew.-%) an Propylenoxid-Einheiten, bezogen auf das Gewicht der entsprechenden Polyoxyalkylenkette, vorliegt,
K steht für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen,
T steht für ein Molekülfragment umfassend mindestens einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht;

worin unabhängig voneinander
p eine ganze Zahl von 1 bis 500 bedeutet und m eine ganze Zahl von 0 bis 500 bedeutet und p und m ein Verhältnis zueinander aufweisen, dass ein maximaler Anteil von 50 Gew.-% (bevorzugt maximal 40 Gew.-%, besonders bevorzugt maximal 30 Gew.-%) an Propylenoxid-Einheiten, bezogen auf das Gewicht der entsprechenden Polyoxyalkylenkette, hat;
K stehen unabhängig voneinander für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen,
T stehen unabhängig voneinander für ein Molekülfragment umfassend mindestens einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht.Very particularly preferred polyether-modified organic compounds are selected from at least one compound of the formula (PE-1a) or (PE-1b) or (PE-1c) or (PE-1d) or (PE-1e) or (PE-1f ) or mixtures thereof,

wherein
at least three groups R stand for a group * - (CH ₂ CH ₂ O) _p - (CHCH ₃ CH ₂ O) _m -KT and the other groups R stand for a hydrogen atom or a group * -KT, in which independently of one another
p is an integer from 1 to 500 and m is an integer from 0 to 500 and p and m have a relationship to each other that a maximum proportion of 50 wt .-% (preferably at most 40 wt .-%, particularly preferably maximum 30% by weight) of propylene oxide units, based on the weight of the corresponding polyoxyalkylene chain, is present,
K stands for a connectivity selected from a covalent bond or from a molecule fragment with two free valences,
T represents a molecular fragment comprising at least one radical * -Si (OR) _x (R ') _3-x , in which R and R' independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) x is 1, 2 or 3;

wherein
at least three groups R stand for a group * - (CH ₂ CH ₂ O) _p - (CHCH ₃ CH ₂ O) _m -KT and the other groups R stand for a hydrogen atom or a group * -KT, in which independently of one another
p is an integer from 1 to 500 and m is an integer from 0 to 500 and p and m have a relationship to each other that a maximum proportion of 50 wt .-% (preferably at most 40 wt .-%, particularly preferably maximum 30% by weight) of propylene oxide units, based on the weight of the corresponding polyoxyalkylene chain, is present,
K stands for a connectivity selected from a covalent bond or from a molecule fragment with two free valences,
T represents a molecular fragment comprising at least one radical * -Si (OR) _x (R ') _3-x , in which R and R' independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) x is 1, 2 or 3;

wherein
at least three groups R stand for a group * - (CH ₂ CH ₂ O) _p - (CHCH ₃ CH ₂ O) _m -KT and the other groups R stand for a hydrogen atom or a group * -KT, in which independently of one another
p is an integer from 1 to 500 and m is an integer from 0 to 500 and p and m have a relationship to each other that a maximum proportion of 50 wt .-% (preferably at most 40 wt .-%, particularly preferably maximum 30% by weight) of propylene oxide units, based on the weight of the corresponding polyoxyalkylene chain, is present,
K stands for a connectivity selected from a covalent bond or from a molecule fragment with two free valences,
T represents a molecular fragment comprising at least one radical * -Si (OR) _x (R ') _3-x , in which R and R' independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) x is 1, 2 or 3;

wherein
at least three groups R represent a group - (CH ₂ CH ₂ O) _p - (CHCH ₃ CH ₂ O) _m -KT and the other groups R stand for a hydrogen atom or a group -KT, in which independently of one another
p is an integer from 1 to 500 and m is an integer from 0 to 500 and p and m have a relationship to each other that a maximum proportion of 50 wt .-% (preferably at most 40 wt .-%, particularly preferably maximum 30% by weight) of propylene oxide units, based on the weight of the corresponding polyoxyalkylene chain, is present,
K stands for a connectivity selected from a covalent bond or from a molecule fragment with two free valences,
T represents a molecular fragment comprising at least one radical * -Si (OR) _x (R ') _3-x , in which R and R' independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) x is 1, 2 or 3;

wherein independently of one another
p is an integer from 1 to 500 and m is an integer from 0 to 500 and p and m have a relationship to each other that a maximum proportion of 50 wt .-% (preferably at most 40 wt .-%, particularly preferably maximum 30% by weight) of propylene oxide units, based on the weight of the corresponding polyoxyalkylene chain;
K independently represent a connectivity selected from a covalent bond or from a molecular fragment having two free valences,
T independently of one another represent a molecular fragment comprising at least one radical * -Si (OR) _x (R ') _3-x , in which R and R' independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl ), x is 1, 2 or 3.

The ethylene oxide and propylene oxide units may be randomly distributed or distributed in a gradient or in at least two blocks.

The previously preferred groups K and T apply to the formulas (PE-1a) to (PE-1f). Most preferably, the structural fragment -KT according to formulas (PE-1a) to (PE-1f) represents a group

The polyether-modified organic compounds of the formula (PE-1) are preferably present in the compositions according to the invention in an amount of from 0.01 to 15.0% by weight, particularly preferably from 0.1 to 8.0% by weight, most preferably from 0.2 to 5.0 wt .-%, most preferably from 0.25 to 2.5 wt .-%, each based on the weight of the total composition.

• (a) Polyether-modifizierte, organische Verbindungen, welche durch Umsetzung von (i) organischen Verbindungen enthaltend mindestens drei Reste, ausgewählt aus Hydroxygruppe und/oder Aminogruppe (insbesondere: aus Hydroxygruppe, primäre Aminogruppe, sekundäre Aminogruppe; besonders bevorzugt Hydroxygruppe(n)) mit (ii) mindestens 3 Moläquivalenten mindestens eines Polyethers der Formel (I) erhalten werden T-K-A-K'-Y (I) worin A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A, K und K' stehen unabhängig voneinander für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen, T für einen Rest -Si(OR)_x(R')_3-x steht, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, und x für 1, 2 oder 3 steht Y für eine gegenüber eine Hydroxygruppe oder Aminogruppe reaktive Gruppe steht, und
• (b) mindestens eine polare Alkoxysilanverbindung der Formel (SI)
  
  worin G für eine (C₁ bis C₃)-Alkylengruppe steht, K'' für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen steht, R¹ für ein Molekülfragment steht, umfassend mindestens einen polaren Substituenten ausgewählt aus mindestens einem Vertreter der Gruppe, die gebildet wird aus quaternisierten Ammonium-Resten Aminogruppen anionischen Resten x für 1, 2 oder 3 steht, R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen steht, und
• (c) mindestens eine farbgebende Verbindung.

According to the invention, those cosmetic agents are preferred which are contained in a cosmetically acceptable carrier

• (a) polyether-modified organic compounds which are obtained by reacting (i) organic compounds containing at least three radicals selected from hydroxyl group and / or amino group (in particular: hydroxyl group, primary amino group, secondary amino group, particularly preferably hydroxy group (s)) with (ii) at least 3 molar equivalents of at least one polyether of formula (I) are obtained TKA-K'-Y (I) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A, K and K 'are independently selected for connectivity from a covalent bond or from a molecular fragment with two free valences, T is a radical -Si (OR) _x (R ') _3-x , wherein R and R' independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), and x is 1 , 2 or 3 Y is a group reactive with a hydroxy group or amino group, and
• (b) at least one polar alkoxysilane compound of the formula (SI)
  
  wherein G is a (C ₁ to C ₃ ) alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized ammonium radicals, amino groups of anionic radicals x is 1, 2 or 3, R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl ) stands, and
• (c) at least one coloring compound.

The indication of the molar equivalents refers to the molar amount of the organic compound used.

For the radicals A, K, K 'and T, the preferred embodiments mentioned under formula (PE-1) apply.

• – eine Isocyanatfunktion, (die Isocyanatfunktion ist besonders bevorzugt)
• – eine Gruppe *-Si(OR)_x(R')_3-x worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen und x für 1, 2 oder 3 steht,
• – eine Gruppe *-Si(R)_x(R')_3-x worin R für ein Halogenatom steht (bevorzugt für Chlor oder Brom) und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen und x für 1, 2 oder 3 steht,
• – eine Gruppe T-K-C(0)-O-C(O)-*, worin T und K gemäß Formel (I) definiert sind,
• – eine Gruppe *-C(O)-Hal, worin Hat für Chlor oder Brom steht,
• – eine Epoxygruppe,
• – eine Formylgruppe.

Preferably, the radical Y according to formula (I) is

• An isocyanate function, (the isocyanate function is particularly preferred)
• A group * -Si (OR) _x (R ') _3-x in which R and R' independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl) and x is 1, 2 or 3 stands,
• A group * -Si (R) _x (R ') _3-x in which R is a halogen atom (preferably chlorine or bromine) and R' independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl) and x is 1, 2 or 3,
• A group TKC (O) -OC (O) - *, wherein T and K are defined according to formula (I),
• - a group * -C (O) -Hal, wherein H is chlorine or bromine,
• An epoxy group,
• A formyl group.

The polyether-modified organic compounds of this embodiment are preferably present in the compositions according to the invention in an amount of from 0.01 to 10.0% by weight, more preferably from 0.1 to 2.0% by weight, very particularly preferably 0, 2 to 1.0 wt .-%, each based on the weight of the total composition.

The polyethers of the formula (I) preferably have a molecular weight of from 1 to 200 kDa, more preferably from 1 to 10 kDa.

The polyethers of the formula (I) which can be used in the context of the invention for preparing the polyether-modified organic compounds of component (a) are obtainable by reacting at least one compound of the formula (II): XAX '(II) wherein
A is a polyoxyalkylene chain of ethylene oxide units or ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A,
X and X 'independently represent a structural fragment containing a group OH, NH ₂ or NHR
with at least 2 molar equivalents of a compound of the formula (III) YKT (III) wherein,
Y is a reactive group with respect to -OH, -NH ₂ , -NHR, -NR ₂ ,
K stands for a connectivity selected from a covalent bond or from a molecule fragment with two free valences,
T is a molecule fragment comprising at least one residue -Si (OR) _x (R ') _3-x
wherein R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl), x is 1, 2 or 3.

The indication of the molar equivalents refers to the molar amount of the compound (s) of the formula (II) used.

According to the above preparation process for the preparation of the compounds of the formula (I), the compounds of the formula (II) are, for example, dihydroxy-terminated polyoxyalkylene diols, diaminoterminated polyoxyalkylene diamines, monohydroxy monoamine-terminated polyoxyalkylene monol monoamines, monohydroxy-monoalkoxy-terminated polyoxyalkylene monols or monoamino-monoalkoxy-terminated polyoxyalkylene monoamines, of which the diamines and diols are preferred.

The radicals X and X 'of the formula (II) are preferably, independently of one another, OH, NH ₂ and NHR, particularly preferably OH and NH ₂ . The radical R in the groups NHR and NR _{2 of} the formula (III) preferably represents a linear or branched alkyl group having 1 to 10, preferably 1 to 6, carbon atoms.

The number-average molecular weight of the compound of the formula (II) is preferably 500 to 30,000 g / mol, particularly preferably 1,000 to 20,000, better still 2,000 to 18,000 g / mol, and can be determined, for example, by determination of end groups.

For the radicals A, K, K 'and T, the preferred embodiments mentioned under formula (PE-1) apply.

In the context of this embodiment, preference is given to using at least one compound of the general formula (III-1) as the compound of the formula (III) YK-Si (OR) _x (R ') _3-x (III-1) wherein,
Y is an OH, NH ₂ , NHR and / or NR ₂ reactive group (in particular an isocyanate group, a halogen atom, a carboxylic acid anhydride group, a halocarbonyl group (in particular chlorocarbonyl), an epoxy group, a formyl group),
K as defined under formula (I) (or as the aforementioned preferred connectivities),
R is a (C ₁ to C ₄ ) -alkyl group or a (C ₂ to C ₄ ) -acyl group (in particular ethyl or methyl),
R 'is a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl),
x stands for 1, 2 or 3.

Compounds of general formula (III-1) include all functional silane derivatives capable of reacting with X groups of formula (III-1). Examples are acrylate silanes such as (3-acryloxypropyl) trimethoxysilane, (acryloxymethyl) triethoxysilane and (acryloxymethyl) methyl-dimethoxysilane, isocyanato-silanes such as (3-isocyanatopropyl) trimethoxysilane, (3-isocyanatopropyl) triethoxysilane, (isocyanatomethyl) methyl-dimethoxysilane and (Isocyanatomethyl) trimethoxysilane, aldehyde silanes such as triethoxysilylundecanal and triethoxysilylbutyraldehydes, epoxy silanes such as (3-glycidoxypropyl) trimethoxysilane, anhydride silanes such as 3- (triethoxysilyl) propylsuccinic anhydride, halo-silanes such as chloromethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, and tetraethylsilicate (TEOS) commercially available, for example, from Wacker Chemie GmbH (Burghausen), available from Gelest, Inc. (Morrisville, USA) or ABCR GmbH & Co. KG (Karlsruhe), or prepared by known methods. Particular preference is given to isocyanato-silanes or anhydride-silanes. For a complete conversion of all hydroxy ends with isocyanatosilanes to obtain completely silylated polyethers. In such a case, the group K contains only the atomic group which is in the starting isocyanatosilane between the isocyanato group and the silyl group. Complete conversion of all hydroxy ends with anhydride silanes, for example 3- (triethoxysilyl) propyl succinic anhydride, also gives completely silylated polyethers. The group K 'in such a case contains only the atomic group which is in the starting anhydride silane between the anhydride group and the silyl group.

If the radicals X and X 'in the general formula (II) are OH, NH ₂ or NHR, the reaction with the compounds of the general formula (III) or (III-1) is usually carried out either with elimination of the compound HY - as for example in the case of the reaction of an OH group with a monohalosilane (K = direct bond) - or under addition - such as in the case of reaction of an OH group with an isocyanatoalkylsilane (formation of a urethane).

The radicals X and X 'of the formula (II) are preferably, independently of one another, OH, NH ₂ and NHR, particularly preferably OH and NH ₂ .

The radical R in the groups NHR, NR ₂ and OR of the formula (III-1) preferably represents a linear or branched alkyl group having 1 to 10, preferably 1 to 6, carbon atoms.

In the reaction between the compounds of the formula (I) and the compounds of the formula (II), at least one hydrogen atom, preferably up to four hydrogen atoms of the OH and / or NH ₂ groups, is reacted with one molecule each of the compound of the general formula (II) implemented so that at least monosilylated, in the case of diamino compounds of the general formula (I) up to four times silylated polyether arise.

worin
A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A,
R und R'' unabhängig voneinander stehen für Methylen, Ethan-1,2-diyl, Propan-1,2-diyl, Propan-1,3-diyl, Butan-1,2-diyl, Butan-1,3-diyl, Butan-1,4-diyl, Phenylen,
R¹ für eine (C₁ bis C₆)-Alkylgruppe, ein Wasserstoffatom oder eine Gruppe R³ _3-x(R²O)_xSi-K- steht,
R² für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) steht,
R³ für eine (C₁ bis C₆)-Alkylgruppe oder eine Arylgruppe (insbesondere Methyl) steht,
x für 1, 2, 3 (insbesondere 3) steht.Very particularly preferred polyethers for preparing the polyether-modified organic compounds according to the invention are selected from at least one compound of the formulas (I-1a) or (I-1b)

wherein
A denotes a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A,
R and R "independently represent methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl , Butane-1,4-diyl, phenylene,
R ^{1 is} a (C ₁ to C ₆ ) -alkyl group, a hydrogen atom or a group R ³ _3-x (R ² O) _x Si-K-,
R ^{2 is} a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl),
R ^{3 is} a (C ₁ to C ₆ ) -alkyl group or an aryl group (in particular methyl),
x is 1, 2, 3 (in particular 3).

Said water-soluble, polyether-modified, organic polymer having at least one polyether structural unit is selected in a preferred embodiment from one or more linear polyethene of the formula (PE-2) TKA-K'-T (PE-2) wherein
A denotes a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A,
K and K 'independently represent a connectivity selected from a covalent bond or from a molecular fragment having two free valences,
T and T 'represent a molecular fragment comprising at least one radical -Si (OR) _x (R') _3-x
wherein R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl), x is 1, 2 or 3.

worin
A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A,
K für eine kovalente Bindung, eine Oxygruppe, eine Iminogruppe oder mindestens eine der folgenden Konnektivitäten (K1) bis (K10)

worin
R und R'' unabhängig voneinander stehen für Methylen, Ethan-1,2-diyl, Propan-1,2-diyl, Propan-1,3-diyl, Butan-1,2-diyl, Butan-1,3-diyl, Butan-1,4-diyl, Phenylen und
R' ein Wasserstoffatom oder eine (C₁ bis C₄)-Alkylgruppe bedeutet,
R''' unabhängig voneinander eine (C₁ bis C₄)-Alkylgruppe oder eine Arylgruppe bedeutet.Very particularly preferred linear polyethers are selected from at least one compound of the formulas (PE-2a), (PE-2b), (PE-2c), (PE-2d) or (PE-2e)

wherein
A denotes a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A,
K for a covalent bond, an oxy group, an imino group or at least one of the following connectivities (K1) to (K10)

wherein
R and R "independently represent methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl Butane-1,4-diyl, phenylene and
R 'represents a hydrogen atom or a (C ₁ to C ₄ ) -alkyl group,
R '''independently of one another is a (C ₁ to C ₄ ) -alkyl group or an aryl group.

R and R "independently represent methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl , Butane-1,4-diyl, phenylene,
R ^{1 is} a group R ³ _3-x (R ² O) _x Si-K-,
R ^{2 is} a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl),
R ^{3 is} a (C ₁ to C ₆ ) -alkyl group or an aryl group (in particular methyl),
x is 1, 2, 3 (in particular 3).

A is therefore preferably a structural fragment of the formula (A1) according to formula (PE-2) or formula (PE-2a) to (PE-2e) * - (OCH ₂ CH ₂ ) _n - (OCH ₂ CH (CH ₃ )) _m - * (A1) wherein
n is an integer from 100 to 10,000,
m is an integer from 0 to 10,000 and
the structural fragment of the formula (A1) has a maximum proportion of 50% by weight of propylene oxide units, based on the weight of the structural fragment (A1).

The polyether-modified organic compounds of the formula (PE-2) are preferably present in the compositions according to the invention in an amount of from 0.01 to 15.0% by weight, particularly preferably from 0.1 to 8.0% by weight, most preferably from 0.2 to 5.0 wt .-%, most preferably from 0.25 to 2.5 wt .-%, each based on the weight of the total composition.

• (i) welche an der Oberfläche mit Polyethern modifiziert sind, wobei die Polyether eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten umfassen, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht der Polyoxyalkylenkette,
• (ii) mindestens einen Rest *-Si(OR)_x(R')_3-x aufweisen, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht.

In a further embodiment, said water-soluble polymer of component (a) of the agent according to the invention is selected from solid particles,

• (i) which are surface-modified with polyethers, the polyethers comprising a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum of 50% by weight of propylene oxide units, based on the weight of the polyoxyalkylene chain .
• (ii) have at least one radical * -Si (OR) _x (R ') _3-x , wherein R and R' independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl), x stands for 1, 2 or 3.

The framework of the solid particles is preferably selected from aluminates, silicates, aluminum silicates, zinc oxide, titanium dioxide and SiO ₂ , in particular aluminates, silicates, aluminum silicates and silica gel. Likewise according to the invention are in each case mixtures of these preferred or particularly preferred solid particles.

Particularly preferred aluminates are selected from alpha-alumina, beta-alumina, gamma-alumina and mixtures thereof.

Particularly preferred aluminum silicates (also called aluminosilicates) are selected from phyllosilicates, tectosilicates.

Preferred phyllosilicates are selected from kaolins (here in particular kaolinite, dickite, halloysite and nacrite), serpentine, talc, pyrophyllite, montmorillonite, quartz, bentonite, mica (here in particular under illite, muscovite, paragonite, phlogopite, biotite, lepidolite, margarite , Smectite (here in particular montmorillonite, saponite, nontronite, hectorite)).

Preferred tectosilicates are selected from feldspar minerals (especially albite, orthoclase, anorthite, leucite, sodalite, hauyne, labradorite, lasurite, nosean, nepheline), zeolites.

Zeolites are natural or synthetic crystalline aluminum silicates of alkali or alkaline earth metals. Zeolites consist of SiO ₄ and AlO ₄ tetrahedra linked by four, six, eight, or twelve oxygen rings, resulting in cavities extending through the entire zeolite crystal. Among the preferred zeolites are the zeolites of the type A, K, L, PL, O, T, X, Y and Ω and mixtures thereof. Particularly preferred zeolites are selected in particular under zeolite A (here in particular under Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]), Ca ₅ Na ₅ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ], [K ₁₂ (AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]), zeolite X (here in particular under Na ₈₅ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]), Ca ₄₀ Na ₆ (AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ) Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]), zeolite Y (here in particular under Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ], Na ₅₆ [(AlO ₂ ) ₅₆ ( SiO ₂ ) ₁₃₆ ]), ZSM-5 (here in particular Na ₃ [(AlO ₂ ) ₃ (SiO ₂ ) ₉₃ ]), mordenite, silicalite (SiO ₂ ) ₉₆ .

• (a) Polyether-modifizierte Feststoffpartikel, welche durch Umsetzung von Hydroxygruppen-haltigen Feststoffpartikeln mit mindestens einem Polyether der Formel (I) erhalten werden T-K-A-K'-T' (I) worin A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A, K und K' stehen unabhängig voneinander für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen, T und T' stehen unabhängig voneinander für ein Molekülfragment, umfassend mindestens einen Rest -Si(OR)_x(R')_3-x worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht wobei höchstens ein Rest aus T oder T' zusätzlich für eine (C₁ bis C₆)-Alkylgruppe, eine Arylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine (C₁ bis C₆)-Alkoxygruppe oder eine (C₂ bis C₆)-Acylgruppe stehen kann, und
• (b) mindestens eine polare Alkoxysilanverbindung der Formel (SI)
  
  worin G für eine (C₁ bis C₃)-Alkylengruppe steht, K'' für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen steht, R¹ für ein Molekülfragment steht, umfassend mindestens einen polaren Substituenten ausgewählt aus mindestens einem Vertreter der Gruppe, die gebildet wird aus quaternisiertem Stickstoffatom Aminogruppen anionischen Resten x für 1, 2 oder 3 steht, R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen steht, und
• (c) mindestens eine farbgebende Verbindung.

According to the invention, those cosmetic agents are preferred which are contained in a cosmetically acceptable carrier

• (A) Polyether-modified solid particles, which are obtained by reacting hydroxy-containing solid particles with at least one polyether of formula (I) TKA-K'-T '(I) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A, K and K 'are independently selected for connectivity from a covalent bond or from a molecule fragment with two free valences, T and T 'independently represent a molecular fragment comprising at least one radical -Si (OR) _x (R') _3-x in which R and R 'independently of one another (C ₁ to C ₄ ) alkyl group (especially methyl or ethyl), x is 1, 2 or 3 wherein at most one radical of T or T 'additionally for a (C ₁ to C ₆ ) alkyl group, an aryl group , an aryl (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) alkoxy group or a (C ₂ to C ₆ ) acyl group, and
• (b) at least one polar alkoxysilane compound of the formula (SI)
  
  wherein G is a (C ₁ to C ₃ ) alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized nitrogen atom, amino groups of anionic radicals x is 1, 2 or 3, R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) stands, and
• (c) at least one coloring compound.

The polyether-modified solid particles are preferably present in the compositions according to the invention in an amount of from 0.01 to 15.0% by weight, preferably from 0.1 to 8.0% by weight, particularly preferably from 0.2 to 5.0 Wt .-%, most preferably from 0.25 to 2.5 wt .-%, each based on the weight of the total composition.

worin die Reste G, K'', R¹, R, R' und die Zahl x wie zuvor beschrieben definiert sind (vide supra).The cosmetic according to the invention contains as compelling component (b) at least one polar alkoxysilane compound of the formula (SI)

wherein the radicals G, K ", R ¹ , R, R 'and the number x are defined as previously described (vide supra).

To compensate for the cationic charge of the radical R ¹ , the agent according to the invention comprises one equivalent of corresponding anions. Suitable inorganic and organic anions, such as chloride, bromide, methyl sulfate, sulfate, hydrogen sulfate, methyl sulfate, triflate, toluenesulfonate, tetrafluoroborate.

In this case, it is preferred according to the invention if, according to formula (SI), the radical R 'is a methyl group and the radical R is an ethyl group.

worin
R und R'' unabhängig voneinander stehen für Methylen, Ethan-1,2-diyl, Propan-1,2-diyl, Propan-1,3-diyl, Butan-1,2-diyl, Butan-1,3-diyl, Butan-1,4-diyl oder Phenylen,
R' ein Wasserstoffatom oder eine (C₁ bis C₄)-Alkylgruppe bedeutet,
R''' unabhängig voneinander eine (C₁ bis C₄)-Alkylgruppe oder eine Arylgruppe bedeutet. The radical K "of the formula (SI) preferably represents a covalent bond, an oxy group, a (C ₁ to C ₆ ) -alkylene group, an imino group or at least one of the following connectivities (K ₁ ) to (K 10)

wherein
R and R "independently represent methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl Butane-1,4-diyl or phenylene,
R 'represents a hydrogen atom or a (C ₁ to C ₄ ) -alkyl group,
R '''independently of one another is a (C ₁ to C ₄ ) -alkyl group or an aryl group.

The radical G according to formula (SI) is preferably a methylene group or a propane-1,3-diyl group, particularly preferably a propane-1,3-diyl group.

The radical R ^{1 of} the formula (SI) particularly preferably comprises at least one quaternized nitrogen atom.

For the preparation of the compounds of the formula (SI), at least one compound of the formula (III) YK-Si (OR) _x (R ') _3-x (III) wherein,
Y is a reactive group with respect to -OH, -NH ₂ , -NHR, -NR ₂ ,
K stands for a connectivity selected from a covalent bond or from a molecule fragment with two free valences,
R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl),
x is 1, 2 or 3,
reacted with at least one compound of the formula (IV), ZR ² (IV) wherein
Z is an -OH, -NH ₂ , -NHR, -NR ₂ group,
R ^{2 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed
quaternized nitrogen atoms (preferably R ² according to formula (SI-1) (vide infra))
amino groups
anionic radicals.

Preferred compounds of the formula (III) are the abovementioned compounds of the formula (III-1) and their representatives (vide supra) which are identified as being particularly preferred.

If the radical Z in the general formula (IV) is OH, NH ₂ or NHR, the reaction with the compounds of the general formula (III) or (III-1) is usually carried out either with elimination of the compound HY - as described, for example, in US Pat Case of reacting an OH group with a monohalosilane (K = direct bond) - or under addition - as for example in the case of the reaction of an OH group with an isocyanatoalkylsilane (formation of a urethane).

The radical Z of the formula (IV) is preferably OH, NH ₂ and NHR, particularly preferably OH or NH ₂ .

Within the scope of a particularly preferred embodiment of the alkoxysilanes of the formula (SI) according to the invention, at least one molecule fragment R ^{1 of} the formula (SI) (for the above-described preparation process also R ^{2 of} the formula (IV)) comprises at least one quaternized nitrogen atom.

In this case, it is again particularly preferred if the molecule fragment R ^{1 of} the formula (SI) (for the above-described preparation process also R ^{2 of} the formula (IV)) in addition to at least one quaternized nitrogen atom additionally comprises at least one hydrocarbon radical having 8 to 20 carbon atoms attached thereto.

worin
R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen,
x für 1, 2 oder 3 steht,
n für 1, 2 oder 3 steht,
X für ein Sauerstoffatom oder eine Gruppe NH steht,
R² für eine Gruppe *-(CH₂)_m-N⁺R³R⁴R⁵ steht,
worin
m steht für 2, 3, 4, 5 oder 6,
R³, R⁴ und R⁵ unabhängig voneinander stehen für (C₁ bis C₂₀)-Alkyl, (C₈ bis C₂₀)-Acyloxy-(C₂ bis C₃)-alkyl, (C₂ bis C₂₀)-Alkenyl, (C₈ bis C₂₀)-Alkanamido-(C₂ bis C₃)-alkyl oder Aryl-(C₁ bis C₄)-alkyl.Very particularly preferred agents according to the invention contain as polar alkoxysilane of the formula (SI) at least one compound of the formula (SI-1)

wherein
R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl),
x is 1, 2 or 3,
n is 1, 2 or 3,
X is an oxygen atom or a group NH,
R ^{2 is} a group * - (CH ₂ ) _m -N ⁺ R ³ R ⁴ R ⁵ ,
wherein
m stands for 2, 3, 4, 5 or 6,
R ³ , R ⁴ and R ⁵ independently of one another represent (C ₁ to C ₂₀ ) -alkyl, (C ₈ to C ₂₀ ) -acyloxy- (C ₂ to C ₃ ) -alkyl, (C ₂ to C ₂₀ ) - Alkenyl, (C ₈ to C ₂₀ ) alkanamido (C ₂ to C ₃ ) alkyl or aryl (C ₁ to C ₄ ) alkyl.

In this case, it is again particularly preferred if the molecule fragment R ^{2 of} the formula (SI-1) additionally comprises, in addition to at least one quaternized nitrogen atom, at least one hydrocarbon radical having 8 to 20 carbon atoms attached thereto.

According to formula (SI-1) and formula (IV) above, R ^{2 is} preferably an (N, N, N-tri (C ₁ to C ₂₀ ) -alkylazanonyl) - (C ₂ to C ₆ ) -alkyl group, a ( N - [(C ₈ to C ₂₀ ) acyloxy (C ₂ to C ₃ ) alkyl] -N, N-dimethylazanonyl) - (C ₂ to C ₆ ) alkyl group, an (N, N-di [(C ₈ to C ₂₀ ) acyloxy (C ₂ to C ₃ ) alkyl] -N-methyl] azanoyl) - (C ₂ to C ₆ ) alkyl group, a (N, N-dimethyl-N- (C ₈ to C ₂₀ ) -alkylazanonyl) - (C ₂ to C ₆ ) alkyl group, (N, N-dimethyl-N-benzylazanonyl) - (C ₂ to C ₆ ) alkyl group, (N, N-dimethyl-N- (C ₈ to C ₂₀ ) -alkanamido (C ₂ to C ₃ ) -alkyl-azaniumyl) - (C ₂ to C ₆ ) -alkyl group or (N-methyl-N, N-di (C ₈ to C ₂₀ ) -alkanamidoethyl- azaniumyl) - (C ₂ to C ₃ ) alkyl group.

To compensate for the cationic charge of the radical R ² , the agent according to the invention comprises corresponding anions.

Within the scope of a preferred embodiment of the alkoxysilanes of the formula (SI) according to the invention, at least one molecule fragment R ^{1 of} the formula (SI) (for the above-described preparation process also R ^{2 of} the formula (IV)) comprises at least one amino group, preferably at least one tertiary amino group.

In this case, it is again particularly preferred if the molecule fragment R ^{1 of} the formula (SI) (for the above-described preparation process also R ^{2 of} the formula (IV)) in addition to at least one quaternized nitrogen atom additionally comprises at least one hydrocarbon radical having 8 to 20 carbon atoms attached thereto.

worin
R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen,
x für 1, 2 oder 3 steht,
n für 1, 2 oder 3 steht,
X für ein Sauerstoffatom oder eine Gruppe NH steht,
R² steht für eine Gruppe *-(CH₂)_m-NR³R⁴ worin
m steht für 2, 3, 4, 5 oder 6,
R³ und R⁴ unabhängig voneinander stehen für (C₁ bis C₂₀)-Alkyl, (C₈ bis C₂₀)-Acyloxy-(C₂ bis C₃)-alkyl, (C₂ bis C₂₀)-Alkenyl, (C₈ bis C₂₀)-Alkanamido-(C₂ bis C₃)-alkyl oder Aryl-(C₁ bis C₄)-alkyl.Preferred agents according to the invention contain as polar alkoxysilane of the formula (SI) at least one compound of the formula (SI-1a)

wherein
R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl),
x is 1, 2 or 3,
n is 1, 2 or 3,
X is an oxygen atom or a group NH,
R ² represents a group * - (CH ₂ ) _m -NR ³ R ⁴ in which
m stands for 2, 3, 4, 5 or 6,
R ³ and R ⁴ independently of one another represent (C ₁ to C ₂₀ ) -alkyl, (C ₈ to C ₂₀ ) -acyloxy- (C ₂ to C ₃ ) -alkyl, (C ₂ to C ₂₀ ) -alkenyl, ( C ₈ to C ₂₀ ) -alkanamido (C ₂ to C ₃ ) -alkyl or aryl- (C ₁ to C ₄ ) -alkyl.

In this case, it is again preferred if the molecule fragment R ^{2 of} the formula (SI-1a) additionally comprises, in addition to at least one said amino group, at least one hydrocarbon radical having 8 to 20 carbon atoms.

According to formula (SI-1a) and formula (IV) above, R ^{2 is} preferably an (N, N-di (C ₁ to C ₂₀ ) -alkylamino) - (C ₂ to C ₆ ) -alkyl group, a (N- [(C ₈ to C ₂₀ ) acyloxy (C ₂ to C ₃ ) alkyl] -N-methylamino) - (C ₂ to C ₆ ) alkyl group, an (N, N-di [(C ₈ to C ₂₀ ) acyloxy (C ₂ to C ₃ ) alkyl] amino) - (C ₂ to C ₆ ) alkyl group, a (N-methyl-N- (C ₈ to C ₂₀ ) alkylamino) - (C ₂ to C ₆ ) -alkyl group, (N-methyl-N-benzylamino) - (C ₂ to C ₆ ) -alkyl group, (N-methyl-N- (C ₈ to C ₂₀ ) -alkanamido (C ₂ to C ₃ ) - alkylamino) - (C ₂ to C ₆ ) alkyl group or (N, N-di (C ₈ to C ₂₀ ) alkanamidoethylamino) - (C ₂ to C ₃ ) alkyl group.

worin
R³ steht für Methyl, Ethyl oder Benzyl,
R⁴ und R⁵ stehen unabhängig voneinander für eine Methylgruppe, eine Ethylgruppe, eine (C₈ bis C₂₂)-Alkylgruppe, eine (C₈ bis C₂₂)-Alkenylgruppe, eine 2-((C₈ bis C₂₂)-Alkylcarbonyloxy)ethylgruppe, eine 2-((C₈ bis C₂₂)-Alkenylcarbonyloxy)ethylgruppe, eine (C₈ bis C₂₂)-Alkylamido(C₂ bis C₃)-alkylgruppe.Preferably, said polar trialkoxysilane compounds are selected from the following compounds of the formula (SI-1b)

wherein
R ³ is methyl, ethyl or benzyl,
R ⁴ and R ⁵ independently represent a methyl group, an ethyl group, a (C ₈ to C ₂₂ ) alkyl group, a (C ₈ to C ₂₂ ) alkenyl group, a 2 - ((C ₈ to C ₂₂ ) alkylcarbonyloxy ) ethyl group, a 2 - ((C ₈ to C ₂₂ ) alkenylcarbonyloxy) ethyl group, a (C ₈ to C ₂₂ ) alkylamido (C ₂ to C ₃ ) alkyl group.

worin R für eine (C₈ bis C₂₂)-Acylgruppe steht und R³ für Methyl, Ethyl oder Benzyl (insbesondere Methyl) steht;

worin R für eine (C₈ bis C₂₂)-Alkylgruppe steht;

worin R jeweils für eine (C₈ bis C₂₂)-Alkylgruppe steht;

worin R für eine (C₈ bis C₂₂)-Alkylgruppe steht.Among them, the trialkoxysilane compound is again preferably selected from the formulas (SI-1c) to (SI-1f):

wherein R is a (C ₈ to C ₂₂ ) acyl group and R ^{3 is} methyl, ethyl or benzyl (especially methyl);

wherein R is a (C ₈ to C ₂₂ ) alkyl group;

wherein each R is a (C ₈ to C ₂₂ ) alkyl group;

wherein R is a (C ₈ to C ₂₂ ) alkyl group.

Within the scope of one embodiment of the alkoxysilanes according to the invention, at least one molecule fragment R ^{1 of} the formula (SI) (for the described preparation process thereof, likewise R ^{2 of} the formula (IV)) comprises at least one anionic group.

The molecular fragments R ^{1 of} the formula (SI) and R ^{2 of} the formula (IV) and R ^{2 of} the formula (Si-1) each having at least one anionic group are preferably according to the invention a molecule fragment which is 1 to 5, preferably 3 , 4 or 5, deprotonatable acid groups. The anionic groups or the deprotonatable acid groups of the said molecular fragments R ^{1 of} the formula (SI) and R ^{2 of} the formula (IV) and R ^{2 of} the formula (Si-1) are preferably selected from carboxyl group and / or sulfonic acid group and / or phosphate or their respective salt forms (in particular carboxyl group and / or sulfonic acid group or their respective salt forms, particularly preferably carboxyl group or its salt form).

In one possible embodiment, the molecule fragment R ^{1 of} the formula (SI) and R ^{2 of} the formula (IV) and R ^{2 of} the formula (Si-1) contains at least one, preferably at least two, more preferably 1 to 5, especially 2 to 5 , in particular 2, 3, 4 or 5 carboxymethyl units. In a very particularly preferred embodiment, the said molecular fragment is an ethylenediaminetriacetate unit which is covalently bound via one of its nitrogen atoms to the connectivity K "of the formula (SI).

Preferably, the molecule fragment R ^{1 of} the formula (SI) contains a group * -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ] in which
B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane -1,3-diyl, butane-1,4-diyl),
B 'is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, Butane-1,3-diyl, butane-1,4-diyl),
M is independently of one another a hydrogen atom or one equivalent of a mono- or polyvalent cation,
y is 1 or 2 (preferably 1).

When the above group is acid, the group M is a hydrogen atom. The fragments -COOH in this case form a carboxyl group. When the above group is in its salt form (carboxylate), M is one equivalent of a monovalent or polyvalent cation. The monovalent or polyvalent cation M ^{z +} with a charge number z of one or higher serves merely to compensate for the simply negative charge of the carboxylate present during salt formation, for reasons of electroneutrality. The equivalent of the corresponding cation to be used is 1 / z. The fragment -COOM in the case of salt formation stands for the group: -COO ^- 1 / z (M ^{z +} )

As mono- or polyvalent cations M ^{z +} are in principle all cations in question, which are physiologically compatible. In particular, these are metal cations of the physiologically acceptable metals from groups Ia, Ib, IIa, IIb, IIIb, VIa or VIII of the Periodic Table of the Elements, ammonium ions, as well as cationic organic compounds with quaternized nitrogen atom. The latter are, for example, by protonation of primary, secondary or tertiary organic amines with an acid, such as. B. formed with compounds of the above group R ^d in its acidic form, or by permanent quaternization of said organic amines. Examples of these cationic organic ammonium compounds are 2-ammonioethanol and 2-trimethylammonioethanol. M is preferably a hydrogen atom, an ammonium ion, an alkali metal ion, half an equivalent of an alkaline earth metal ion or half an equivalent of a zinc ion, more preferably a hydrogen atom, an ammonium ion, a sodium ion, a potassium ion, ½ calcium ion, ½ magnesium ion or ½ zinc ion.

A preferred molecular fragment R ¹ of formula (SI) follows the general formula * -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ] in which
B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane -1,3-diyl, butane-1,4-diyl),
B 'is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, Butane-1,3-diyl, butane-1,4-diyl) or an N, N-bis (C ₁ to C ₆ ) alkylene-N-carboxymethyl,
M is independently of one another a hydrogen atom or one equivalent of a mono- or polyvalent cation,
y is 1 or 2 (preferably 1).

For the remainder M of the above formula, what has been said above (vide supra) applies.

Particularly preferred agents of this embodiment have polyether-modified organic compounds containing at least one polyether having at least one molecule fragment R ¹ in formula (SI) of said general formula * -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ] contain.

Particularly preferred molecular fragments R ¹ of formula (SI) having the formula * -B - [(N (CH ₂ COOM) -B ') _y -N (CH ₂ COOM) ₂ ] are selected from at least one member of the group formed is prepared from 3-N-carboxymethyl-N- (2'-N ', N'-di (carboxymethylamino) ethyl) -aminopropyl (B = propane-1,3-diyl, B' = ethane-1,2-diyl, y = 1, M as above), 3-N-carboxymethyl-N- (2'-N ', N'di (carboxymethylamino) ethyl) -N'-carboxymethylamino-ethyl) -aminopropyl (B = propane-1,3 -diyl, B '= ethane-1,2-diyl, y = 2, M as above). In this case, 3-N-carboxymethyl-N- (2'-N ', N'-di (carboxymethylamino) ethyl) aminopropyl is very particularly preferred.

worin
B für einen (C₁ bis C₆)-Alkylen-Rest (vorzugsweise für Ethan-1,2-diyl, Propan-1,2-diyl, Propan-1,3-diyl, Butan-1,2-diyl, Butan-1,3-diyl, Butan-1,4-diyl) steht,
B' für einen (C₁ bis C₆)-Alkylen-Rest (vorzugsweise für Ethan-1,2-diyl, Propan-1,2-diyl, Propan-1,3-diyl, Butan-1,2-diyl, Butan-1,3-diyl, Butan-1,4-diyl) oder einen N,N-Bis(C₁ bis C₆)-Alkylen-N-carboxymethyl steht,
M unabhängig voneinander für ein Wasserstoffatom oder ein Äquivalent eines ein- oder mehrwertigen Kations,
R² und R³ unabhängig voneinander stehen für eine (C₁ bis C₄)-Alkylgruppe (insbesondere Methyl oder Ethyl),
x eine ganze Zahl 1, 2 oder 3 (insbesondere 3) bedeutet,
K steht für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen,
R unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) oder eine (C₁ bis C₆)-Alkoxygruppe (insbesondere Methoxy oder Ethoxy) steht.Very particularly preferred polar alkoxysilanes are selected from at least one compound of the formula (SI-2)

wherein
B is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane -1,3-diyl, butane-1,4-diyl),
B 'is a (C ₁ to C ₆ ) -alkylene radical (preferably ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, Butane-1,3-diyl, butane-1,4-diyl) or an N, N-bis (C ₁ to C ₆ ) alkylene-N-carboxymethyl,
M is independently of one another a hydrogen atom or one equivalent of a mono- or polyvalent cation,
R ² and R ³ independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl),
x is an integer 1, 2 or 3 (in particular 3),
K stands for a connectivity selected from a covalent bond or from a molecule fragment with two free valences,
R independently of one another is a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) or a (C ₁ to C ₆ ) -alkoxy group (in particular methoxy or ethoxy).

For the above-mentioned formula (SI-2), the preferred embodiments apply to the aforementioned preferred features for B, B ', M and R mutatis mutandis.

• (1) aus mindestens einem Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusätzlich mindestens einer Kupplerkomponente und/oder
• (2) aus mindestens einem direktziehenden Farbstoff und/oder
• (3) aus mindestens einer Vorstufe naturanaloger Farbstoffe.

The coloring compounds according to the present invention are preferably selected

• (1) at least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or
• (2) from at least one direct dye and / or
• (3) from at least one precursor of naturally-colored dyes.

wobei

• – G' steht für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen (C₁ bis C₄)-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G² steht für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest oder einen (C₁ bis C₄)-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Hydroxyalkoxyrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Acetylaminoalkoxyrest, einen Mesylamino-(C₁ bis C₄)-alkoxyrest oder einen (C₁ bis C₄)-Carbamoylaminoalkoxyrest;
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom, einen (C₁ bis C₄)-Alkylrest oder einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

It is inventively preferred to use as a developer component, a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

• G 'represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy (C ₁ to C ₄ ) alkyl, 4'-aminophenyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group, a phenyl or a 4'-aminophenyl;
• G ² represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy (C ₁ to C ₄ ) alkyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -hydroxyalkoxy radical, a (C ₁ to C ₄ ) -alkoxy- (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -acetylaminoalkoxy radical, a mesylamino (C ₁ to C ₄ ) alkoxy or (C ₁ to C ₄ ) carbamoylaminoalkoxy;
• G ⁴ represents a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl radical or a (C ₁ to C ₄ ) -alkoxy (C ₁ to C ₄ ) -alkyl radical, or
• When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Particularly preferred p-phenylenediamines of formula (E1) are selected from one or more compounds of the group formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine , 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine , N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N Bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- ( α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N Dimethyl 3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) - p-phenylenediamine, N-phenyl-p-phenyle ndiamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4 -Amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

Very particularly preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) - p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole) 1-yl) propyl] amine, as well as the physiologically acceptable salts of these compounds.

It may be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen (C₁ bis C₄)-Alkylrest, durch einen (C₁ bis C₄)-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder (C₁ bis C₈)-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G', G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen (C₁ bis C₄)-Alkylrest, mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.

Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

• - Z ¹ and Z ² independently represent a hydroxyl or NH ₂ radical, which is optionally substituted by a (C ₁ to C ₄ ) -alkyl radical, by a (C ₁ to C ₄ ) -hydroxyalkyl radical and / or by a bridge Y is substituted or which is optionally part of a bridging ring system,
• - The bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be substituted by one or more hydroxyl or (C ₁ to C ₈ ) alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, - (C ₁ to C ₄ ) -aminoalkyl radical or a direct compound for bridging Y,
• G ', G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a (C ₁ to C ₄ ) -alkyl radical, with the proviso that the compounds of the formula (E2) contain only one bridge Y per molecule.

The substituents used in formula (E2) are defined according to the invention analogously to the above statements.

Preferred dinuclear developing agents of the formula (E2) are in particular selected from at least one of the following compounds: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino -propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) - tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (4- (methylamino) phenyl) tetramethylenediamine, N , N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis (4 '-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis ( 2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (E2) are selected from N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol , Bis (2-hydroxy-5-aminophenyl) -methane, 1,3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest, einen Hydroxy-(C₁ bis C₄)-alkylaminorest, einen (C₁ bis C₄)-Hydroxyalkoxyrest, einen (C₁ bis C₄)-Hydroxyalkyl-(C₁ bis C₄)-aminoalkylrest oder einen (Di-[(C₁ bis C₄)-alkyl]amino)-(C₁ bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest oder einen (C₁ bis C₄)-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

Furthermore, it is inventively preferred to use as developer component at least one p-aminophenol derivative or one of its physiologically acceptable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

• G ¹³ represents a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl, (C ₁ to C ₄ ) aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, (C ₁ to C ₄ ) hydroxyalkoxy, a (C ₁ to C ₄ ) hydroxyalkyl (C ₁ to C ₄ ) aminoalkyl radical or a (di - [(C ₁ to C ₄ ) alkyl] amino) - (C ₁ to C ₄ ) alkyl radical, and
• G ¹⁴ is a hydrogen or halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical or a (C ₁ to C ₄ ) -cyanoalkyl radical,
• G ¹⁵ is hydrogen, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (E3) are defined according to the invention analogously to the above statements.

Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino 2- (diethylaminomethyl) -phenol.

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component is preferably selected from heterocyclic developer components, such as pyrimidine derivatives, pyrazole derivatives, or their physiologically acceptable salts.

worin

• – G¹⁷, G¹⁸ und G¹⁹ unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxygruppe oder eine Aminogruppe steht und
• – G²⁰ für eine Hydroxygruppe oder eine Gruppe -NG²¹G²² steht, worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis Ca)-Monohydroxyalkylgruppe,

mit der Maßgabe, dass maximal zwei der Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ eine Hydroxygruppe bedeuten und höchstens zwei der Reste G¹⁷, G¹⁸ und G¹⁹ für ein Wasserstoffatom stehen. Dabei ist es wiederum bevorzugt, wenn gemäß Formel (E4) mindestens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Gruppe -NG²¹G²² stehen und höchstens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Hydroxygruppe stehen.Preferred pyrimidine derivatives are selected according to the invention from compounds of the formula (E4) or their physiologically tolerated salts,

wherein

• G ¹⁷ , G ¹⁸ and G ¹⁹ independently of one another represent a hydrogen atom, a hydroxy group, a (C ₁ to C ₄ ) alkoxy group or an amino group and
• G ^{20 is} a hydroxy group or a group -NG ²¹ G ²² , in which G ²¹ and G ²² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C 20) monohydroxyalkyl group,

with the proviso that a maximum of two of the groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 is} a hydroxy group and at most two of the radicals G ¹⁷ , G ¹⁸ and G ^{19 are} a hydrogen atom. In this case, it is again preferred if, according to formula (E4), at least two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a group -NG ²¹ G ²² and at most two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a hydroxy group.

Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5 , 6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

worin

• – G²³, G²⁴, G²⁵ stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte Aryl-(C₁ bis C₄)-alkylgruppe, mit der Maßgabe dass, wenn G²⁵ für ein Wasserstoffatom steht, G²⁷ neben den vorgenannten Gruppen zusätzlich für eine Gruppe -NH₂ stehen kann,
• – G²⁶ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis Ca)-Monohydroxyalkylgruppe oder eine (C₂ bis C₄)-Polyhydroxyalkylgruppe und
• – G²⁷ steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Monohydroxyalkylgruppe, insbesondere für ein Wasserstoffatom oder eine Methylgruppe.

Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),

wherein

• G ²³ , G ²⁴ , G ²⁵ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -monohydroxyalkyl group, a (C ₂ to C ₄ ) -polyhydroxyalkyl group, a optionally substituted aryl group or an optionally substituted aryl (C ₁ to C ₄ ) -alkyl group, with the proviso that when G ^{25 is} a hydrogen atom, G ^{27 may} additionally be a group -NH _{2 in} addition to the abovementioned groups,
• G ²⁶ represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to Ca) monohydroxyalkyl group or a (C ₂ to C ₄ ) polyhydroxyalkyl group and
• G ²⁷ represents a hydrogen atom, an optionally substituted aryl group, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -monohydroxyalkyl group, in particular a hydrogen atom or a methyl group.

Preferably in formula (E5) the radical -NG ²⁵ G ²⁶ binds to the 5 position and the radical G ²⁷ to the third position of the pyrazole cycle.

Particularly preferred pyrazole derivatives are in particular the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5- Diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3 phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4 5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methyl-pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4 , 5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4, 5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, and their physiologically acceptable salts ,

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (E1) to (E5): Examples of (C ₁ to C ₄ ) -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , - CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ . Examples of (C ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group. Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CHCH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with the group -CH ₂ CH ₂ OH being preferred. A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples. Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ . Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ . Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ . Examples of (C ₁ to C ₄ ) trialkylammonium groups are -N ⁺ (CH ₃ ) ₃ , -N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₃ ), -N ⁺ (CH ₃ ) (CH ₂ CH ₃ ) ₂ , Examples of (C ₁ to C ₄ ) -hydroxyalkylamino radicals are -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH. Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ), -CH ₂ CH ₂ CH ₂ -O- CH (CH ₃ ). Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CHCH (OH) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH. Examples of (C ₁ to C ₄ ) -acetylaminoalkoxy radicals are -O-CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ CH ₂ NHC (O ) CH ₃ , -O-CH ₂ CH (NHC (O) CH ₃ ) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH ₃ . Examples of (C ₁ to C ₄ ) -carbamoylaminoalkoxy radicals are -O-CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ . Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

Examples of (C ₁ to C ₄ ) -cyanoalkyl radicals are -CH ₂ CN, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ CH ₂ CN. Examples of (C ₁ to C ₄ ) -hydroxyalkylamino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH. Examples of di [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N ( CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ . An example of aryl groups is the phenyl group. Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component. Couplers are preferably cyclic compounds which carry on cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. When the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho position or meta position to each other.

• – m-Aminophenol und/oder dessen Derivate,
• – m-Diaminobenzol und/oder dessen Derivate,
• – o-Diaminobenzol und/oder dessen Derivate,
• – o-Aminophenolderivate, wie beispielsweise o-Aminophenol,
• – Naphthalinderivate mit mindestens einer Hydroxygruppe,
• – Di- beziehungsweise Trihydroxybenzol und/oder deren Derivate,
• – Pyridinderivate,
• – Pyrimidinderivate,
• – Monohydroxyindol-Derivate und/oder Monoaminoindol-Derivate,
• – Monohydroxyindolin-Derivate und/oder Monoaminoindolin-Derivate,
• – Pyrazolonderivate, wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin oder 6-Amino-benzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin, Gemische aus zwei oder mehrer Verbindungen aus einer oder mehrerer dieser Klassen sind im Rahmen dieser Ausführungsform ebenso erfindungsgemäß.

Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:

• M-aminophenol and / or its derivatives,
• M-diaminobenzene and / or its derivatives,
• O-diaminobenzene and / or its derivatives,
• O-aminophenol derivatives, such as o-aminophenol,
• Naphthalene derivatives having at least one hydroxy group,
• Di- or trihydroxybenzene and / or derivatives thereof,
• - pyridine derivatives,
• - pyrimidine derivatives,
• Monohydroxyindole derivatives and / or monoamine indole derivatives,
• Monohydroxyindoline derivatives and / or monoaminoindoline derivatives,
• Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
• - Chinoxalinderivate such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, mixtures of two or more compounds from one or more of these classes are also within the scope of this embodiment according to the invention.

worin
G¹ und G² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine Amino-(C₁ bis C₅)-alkylgruppe, eine (C₁ bis C₆)-Dialkylamino-(C₁ bis C₆)-alkylgruppe oder eine (C₁ bis C₆)-Alkoxy-(C₁ bis C₆)-alkylgruppe, wobei G¹ und G² gemeinsam mit dem Stickstoffatom einen fünfgliedrigen, sechsgliedrigen oder siebengliedrigen Ring bilden können,
G³ und G⁴ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe, eine (C₁ bis C₆)-Alkyox-(C₂ bis C₆)-alkoxygruppe, eine Arylgruppe oder eine Heteroarylgruppe.The m-aminophenols or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K1) and / or from at least one physiologically tolerated salt of a compound of the formula (K1),

wherein
G ¹ and G ² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) -alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, an aryl (C ₁ to C ₆ ) alkyl group, an amino (C ₁ to C ₅ ) alkyl group, a (C ₁ to C ₆ ) dialkylamino (C ₁ to C ₆ ) alkyl group or a (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) -alkyl group, where G ¹ and G ² together with the nitrogen atom can form a five-membered, six-membered or seven-membered ring,
G ³ and G ⁴ independently represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group, a (C ₁ to C ₆ ) -alkoxy (C ₂ to C ₆ ) alkoxy group, an aryl group or a heteroaryl.

Particularly preferred m-aminophenol coupler components are selected from at least one compound selected from the group consisting of m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6 -methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4 -methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) - benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable salts of all the abovementioned compounds.

worin
G⁵, G⁶, G⁷ und G⁸ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Heteroaryl-(C₁ bis C₄)-alkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bilden
G⁹ und G¹⁰ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe, eine ω-(2,4-Diaminophenyl)-(C₁ bis C₄)-alkylgruppe, eine ω-(2,4-Diaminophenyloxy)-(C₁ bis C₄)-alkoxygruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxy-(C₂ bis C₄)-alkoxygruppe, eine Arylgruppe, eine Heteroarylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The m-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerated salt of a compound of the formula (K2),

wherein
G ⁵ , G ⁶ , G ⁷ and G ⁸ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) -alkenyl group , a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl group, an aryl (C ₁ to C ₄ ) alkyl group, a heteroaryl (C ₁ to C ₄ ) alkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G ⁹ and G ¹⁰ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group, an ω- (2,4-diaminophenyl) - (C ₁ to C ₄ ) -alkyl group, an ω- (2,4-diaminophenyloxy) - (C ₁ to C ₄ ) alkoxy group, a (C ₁ to C ₄ ) alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) alkoxy (C ₂ to C ₄ ) alkoxy group, an aryl group, a heteroaryl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group formed from m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2- ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2 -methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and the physiologically acceptable salts of all the abovementioned compounds.

worin
G¹¹, G¹², G¹³ und G¹⁴ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Heteroaryl-(C₁ bis C₄)-alkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bilden
G¹⁵ und G¹⁶ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine Carboxylgruppe, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The o-diaminobenzenes or their derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K3) and / or from at least one physiologically tolerated salt of a compound of the formula (K3),

wherein
G ¹¹ , G ¹² , G ¹³ and G ¹⁴ independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group , a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl group, an aryl (C ₁ to C ₄ ) alkyl group, a heteroaryl (C ₁ to C ₄ ) alkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G ¹⁵ and G ¹⁶ independently of one another represent a hydrogen atom, a halogen atom, a carboxyl group, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) Monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Particularly preferred o-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all of the aforementioned compounds.

Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1 , 2,4-trihydroxybenzene.

worin
G¹⁷ und G¹⁸ stehen unabhängig voneinander für eine Hydroxygruppe oder eine Gruppe- NG²¹G²²
worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine Arylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Heteroaryl-(C₁ bis C₄)-alkylgruppe,
G¹⁹ und G²⁰ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Alkoxygruppe.The pyridine derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K4) and / or from at least one physiologically tolerable salt of a compound of the formula (K4),

wherein
G ¹⁷ and G ¹⁸ independently represent a hydroxy group or a group NG ²¹ G ²²
wherein G ²¹ and G ^{22 are} independently a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, an aryl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl group, an aryl (C ₁ to C ₄ ) alkyl group, a heteroaryl (C ₁ to C ₄ ) alkyl group,
G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -alkoxy group.

It is preferred if, according to formula (K4), the radicals G ¹⁷ and G ^{18 are} in the ortho position or in the meta position relative to one another.

Particularly preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino 6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2, 6-dimethoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically acceptable salts of the aforementioned compounds.

Preferred naphthalene derivatives having at least one hydroxyl group are selected from at least one compound of the group formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1 naphthol, 2-hydroxyethyl-1-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene; dihydroxynaphthalene.

worin
G²³ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₅)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe,
G²⁴ steht für eine Hydroxygruppe oder eine Gruppe -NG²⁵G²⁷, worin G²⁵ und G²⁷ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₅)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G²⁵ Wasserstoffatom, ein Halogenatom oder eine (C₁ bis C₄)-Alkylgruppe, mit der Maßgabe, dass G²⁴ in meta-Position oder ortho-Position zum Strukturfragment NG²³ der Formel bindet.The indole derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K5) and / or from at least one physiologically tolerated salt of a compound of the formula (K5),

wherein
G ²³ represents a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₃ to C ₅ cycloalkyl group, a C ₂ to C ₄ alkenyl group, a C ₁ to C ₄ monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group, an aryl (C ₁ to C ₄ ) alkyl group,
G ²⁴ represents a hydroxy group or a group -NG ²⁵ G ²⁷ , in which G ²⁵ and G ²⁷ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₅ ) -cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ^{25 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) alkyl group, with the proviso that G ²⁴ binds in the meta position or ortho position to the structural fragment NG ^{23 of} the formula.

Particularly preferred indole derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the abovementioned compounds.

worin
G²⁸ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₅)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe,
G²⁹ steht für eine Hydroxygruppe oder eine Gruppe -NG³¹G³², worin G³¹ und G³² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₅)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G³⁰ Wasserstoffatom, ein Halogenatom oder eine (C₁ bis C₄)-Alkylgruppe, mit der Maßgabe, dass G²⁹ in meta-Position oder ortho-Position zum Strukturfragment NG²⁸ der Formel bindet.The indoline derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K6) and / or from at least one physiologically tolerable salt of a compound of the formula (K6),

wherein
G ²⁸ represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₅ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group, an aryl (C ₁ to C ₄ ) alkyl group,
G ²⁹ represents a hydroxy group or a group -NG ³¹ G ³² , in which G ³¹ and G ³² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₅ ) -cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ^{30 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) alkyl group, with the proviso that G ²⁹ binds in the meta position or ortho position to the structural fragment NG ^{28 of} the formula.

Particularly preferred indoline derivatives are selected from at least one compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable salts of the aforementioned compounds.

Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2 -Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine and the physiologically acceptable salts of the aforementioned compounds.

Particularly preferred coupler components according to the invention are selected from m-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol , 5- (2'-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, o-aminophenol, m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-bis) hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2 -methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol , 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4- Trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydr oxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the abovementioned compounds.

The coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use oxidation colorant.

In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can stand.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (K1) to (K6): Examples of (C ₁ to C ₄ ) -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ . Examples of (C ₃ to C ₆ ) cycloalkyl groups according to the invention are cyclopropyl, cyclopentyl and cyclohexyl. Examples of (C ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group. Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with the group -CH ₂ CH ₂ OH being preferred.
A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples. Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ . Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ . Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ -O -CH (CH ₃ ) ₂ .
Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkoxy groups are the groups -O-CH ₂ CH ₂ -O-CH ₃ , -O-CH ₂ CH ₂ CH ₂ -O-CH ₃ , -O-CH ₂ CH ₂ -O-CH ₂ CH ₃ , -O-CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -O-CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ , -O-CH ₂ CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ .
Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CH ₂ CH (OH) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.
Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ . An example of aryl groups is the phenyl group, which may also be substituted. Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

• a) mindestens einen heterozyklischen Entwickler ausgewählt aus Pyrazolderivaten (insbesondere 1-(2-hydroxyethyl)pyrazol) und Pyrimidinderivaten (insbesondere 2,4,5,6-Tetrahydroxypyrimidon), mindestens eine Verbindung ausgewählt aus m-Aminophenol oder seiner Derivate als Kuppler,
• b) 4-Amino-3-methylphenol, 5-Amino-2-methylphenol,
• c) p-Toluylendiamin, 4-Amino-3-methylphenol, 5-Amino-2-methylphenol,
• d) 2-(β-Hydroxyethyl)-p-phenylendiamin, 4-Amino-3-methylphenol, 5-Amino-2-methylphenol.

The compositions according to the invention preferably comprise as coloring compound at least one of the following combinations a) to d) of oxidation dye precursors:

• a) at least one heterocyclic developer selected from pyrazole derivatives (in particular 1- (2-hydroxyethyl) pyrazole) and pyrimidine derivatives (especially 2,4,5,6-tetrahydroxypyrimidone), at least one compound selected from m-aminophenol or its derivatives as coupler,
• b) 4-amino-3-methylphenol, 5-amino-2-methylphenol,
• c) p-toluenediamine, 4-amino-3-methylphenol, 5-amino-2-methylphenol,
• d) 2- (β-hydroxyethyl) -p-phenylenediamine, 4-amino-3-methylphenol, 5-amino-2-methylphenol.

The compositions according to the invention contain at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Preferred substantive dyes are nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably used in an amount of 0.001 to 20 wt .-%, based on the total application preparation. The total amount of substantive dyes is preferably at most 20% by weight.

Direct dyes can be further subdivided into anionic, cationic and nonionic substantive dyes.

Anionic substantive dyes: Suitable anionic substantive dyes are, in particular, 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI 15.985, Food Yellow No. 3, FD & C Yellow No. 6), 2,4- Dinitro-1-naphthol-7-sulfonic acid disodium salt (CI 10,316, Acid Yellow 1, Food Yellow No. 1), 2- (indan-1,3-dion-2-yl) quinoline-x, x-sulfonic acid (Mixture from mono- and disulfonic acid) (CI 47,005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt (CI 13,015 Acid Yellow 9), 5-hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (CI 19.140, Food Yellow No. 4, Acid Yellow 23), 3 - [(4-phenylamino) phenyl] azobenzenesulfonic acid, sodium salt (CI 13.065, Ki406, Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (CI 45.350, Acid Yellow 73 D & C Yellow No. 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid, sodium salt (CI 10,385; Acid Orange 3), 4 - [(2,4-Dihydroxyphenyl) azo] -benzenesulfonic acid, sodium salt (CI 14,270; Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (CI 15.510, Acid Orange 7), 4 - [(2,4-dihydroxy-3 - [(2,4-) dimethylphenyl) azo] -phenyl) azo] -benzenesulfonic acid, sodium salt (CI 20,170; Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid, sodium salt (CI 14,710, Acid Red 4) , 4-Hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid disodium salt (CI 14,720; Acid Red No. 14), 6-hydroxy-5 - [(4-sulfonaphth-1-yl) yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (CI 16,255; Ponceau 4R; Acid Red 18), 3-hydroxy-4 - [(4-sulfonaphth-1-yl) azo] -2,7-naphthalenedisulfonic acid trisodium salt (CI 16.185, Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid disodium salt (CI 17,200, Acid Red 33, Red 33), 5- (acetylamino ) -4-hydroxy-3 - [(2-methylphenyl) azo] -2,7-naphthalenedisulfonic acid disodium salt (CI 18.065; Acid Red 35), 2- (3-hydroxy-2,4,5,7- tetraiodo-dibenzopyran-6-on-9-yl) -benzoic acid disodium salt (CI 45,430, Acid Red 51), N- [6- (D. iethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethylethanammonium hydroxide, inner salt, sodium salt (CI 45, 100; Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulfonic acid disodium salt (CI 27.290; Acid Red 73), 2 ', 4', 5 ', 7' Tetrabromo-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' - [9H] xanthene] -3-one disodium salt (CI 45.380; Acid Red 87), 2 ', 4', 5 ', 7'-Tetrabromo-4,5,6,7-tetrachloro-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' [9H] xanthene] -3-one disodium salt (CI 45.410; Acid Red 92 ), 3 ', 6'-dihydroxy-4', 5'-diiodospiro [isobenzofuran-1 (3H), 9 '(9H) -xanthen] -3-one-disodium salt (CI 45425; Acid Red 95), 2- Hydroxy-3 - ((2-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulfonic acid, sodium salt (CI 15,685; Acid Red 184), 3-hydroxy-4- (3-methyl-5-oxo-1-phenyl) 4,5-dihydro-1H-pyrazol-4-ylazo) naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4 - [(4-methyl-2-sulfonphenyl) azo] 2-naphthalenecarboxylic acid calcium salt (CI 15.850: 1; Pigment Red 57: 1), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt (CI 14,700 Food Red No. 1, Ponceau SX, FD & C Red No. 4), 1,4-Bis [ (2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (CI 61.570; Acid Green 25), bis [4- (dimethylamino) phenyl] - (3,7-disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, sodium salt (CI 44,090, Food Green No. 4, Acid Green 50). , Bis [4- (diethylamino) -phenyl] (2,4-disulfophenyl) carbenium inner salt, sodium salt (2: 1) (CI 42.045, Food Blue No. 3, Acid Blue 1), bis [4- (diethylamino ) phenyl] (5-hydroxy-2,4-disulfophenyl) carbenium inner salt, calcium salt (2: 1) (CI 42,051, Acid Blue 3), N- [4 - [(2,4-disulfophenyl) [4 [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadien-1-ylidene] -N-ethylbenzenemethanamine hydroxide, inner salt, sodium salt (CI 42,080, Acid Blue 7), (2-sulfophenyl) di [ 4- (ethyl ((4-sulfophenyl) methyl) amino) phenyl] -carbenium disodium salt betaine (CI 42.090, Acid Blue 9, FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10- anthraquinone-2-sulfonic acid (CI 62.055; Acid Blue 25), 1-amino-4- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid, sodium salt (CI 62045; Acid Blue 62), 2- (1,3 dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene) -2,3-dihydro-3-oxo-1H-indole 5-sulfonic acid disodium salt (CI 73.015; Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenyl) amino] -6 - [(2-methyl-4-sulfophenyl) amino] xanthylium inner salt, sodium salt (CI 45.190, Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (CI 60,730, D & C Violet No. 2, Acid Violet 43), bis [3-nitro- 4 - [(4-phenylamino) -3-sulfophenylamino] -phenyl] -sulfone (CI 10.410; Acid Brown 13), 5-amino-4-hydroxy-6 - [(4-nitrophenyl) -azo] -3 (phenylazo) -2,7-naphthalenedisulfonic acid disodium salt (CI 20,470, Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1-naphthalene sulfonic acid-chromium complex (3: 2) (CI 15,711, Acid Black 52), 4- (acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl ) azo] -1,7 naphthalenedisulfonic acid tetrasodium salt (CI 28,440, Food Black No. 1), 3 ', 3 ", 5', 5" -tetrabromophenolsulfonephthalein (bromophenol blue), 3,4,5,6,3 ', 3'',5' 5 '' - Octabromophenolsulfonphthalein (tetrabromophenol blue). Preferred anionic substantive dyes are those under the international designations or trade names tetrabromophenol blue, Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.

Cationic substantive dyes: Suitable cationic substantive dyes are, in particular, 9- (dimethylamino) -benzo [a] phenoxazine-7-ium chloride (CI 51.175, Basic Blue 6), di [4- (diethylamino) phenyl] [4- ( ethylamino) naphthyl] carbenium chloride (CI 42,595; Basic Blue 7), di (4- (dimethylamino) phenyl) - (4- (methylphenylamino) -naphthalen-1-yl) carbenium chloride (CI 42,563, Basic Blue 8), 3,7-di (dimethylamino) -phenothiazine-5-ium chloride (CI 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI 44.045 Basic Blue 26), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methylsulfate (CI 11, 154; Basic Blue 41), 8-amino- 2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (CI 56.059; Basic Blue No. 99), bis [4- (4 dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride (CI 42,535, Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (CI 42,520, Basic Vio let 2), tri [4- (dimethylamino) -phenyl] carbenium chloride (C.I. 42.555; Basic Violet 3), 2- [3,6- (diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (CI 45,170, Basic Violet 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (CI 42.510 Basic Violet 14), 1,3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI 21.010, Basic Brown 4), 1 - [(4-aminophenyl) azo] -7 - (trimethylammonio) -2-naphthol chloride (CI 12.250; Basic Brown 16), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride, 1 - [(4- Amino-3-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (CI 12.251, Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzylaminium chloride (CI 12,605, Basic Orange 69), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (CI 50.240, Basic Red 2), 1,4-dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1,2,4-triazolium chloride (CI 11.055, Basic Red 22), 2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) -naphthalene chloride (CI 12.245; Basic Red 76), di [4- (dimethylamino) phenyl] iminomethane hydrochloride (C. I. 41.000; Basic Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (CI 48,055, Basic Yellow 11), 3 -Methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (CI 12,719; Basic Yellow 57), bis [4- (dimethylamino) phenyl] phenylcarbenium bisulfate ( 1: 1) (CI 42.040, Basic Green 1), di (4- (dimethylamino) phenyl) -phenylmethanol (CI 42,000, Basic Green 4), 1- (2-morpholiniumpropylamino) -4-hydroxy-9,10-anthraquinone methylsulfate, 1 - [(3- (dimethylpropylaminium) -propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908 , auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

Preferred cationic substantive dyes are included

• (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
• (C) direct dyes containing a heterocycle having at least one quaternary nitrogen atom, as described for example in the EP-A2-998 908 to which reference is made at this point, are called in the claims 6 to 11.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^®, according to the invention are also very particularly preferred cationic direct dyes.

Nonionic substantive dyes: Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes.

Suitable blue nitro dyes are in particular: 1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue 2), 1-methylamino-4- [methyl- (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Blue 6), 1 - [(2,3-dihydroxypropyl) amino] -4- [ethyl (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 9), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl (2-hydroxyethyl) amino] -2- nitrobenzene (HC Blue 10), 4- [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 11), 4- [ethyl (2-hydroxyethyl) - amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylaminobenzoic acid (HC Blue 13) , 1-Amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] - 2-nitrobenzene (HC Violet 2), 1- (2-aminoethylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro -1-phenylamino-benzene.

Suitable red nitro dyes are, in particular: 1-amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (picramic acid) and its salts, 1,4- Diamino-2-nitrobenzene (CI 76.070), 4-amino-2-nitro-diphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13 ), 1-amino-4 - [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2-hydroxyethyl) methylamino] -1- (methylamino) -2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) amino] -5-methyl-2-nitrobenzene, 1-amino- 4- (methylamino) -2-nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) amino] benzene, 4-amino-3-nitrophenol, 4 - [( 2-hydroxyethyl) amino] -3-nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2- nitrobenzene (HC Orange 2), 4- (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Orange 3), 1-amino-5-chloro-4 - [(2 , 3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red 10), 5- Chloro-1,4- [di (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red 11), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3- nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro 4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 2,5-diamino-6-nitropyridine, 6-amino-3 - [(2-hydroxyethyl) amino] -2 -nitropyridine, 3-amino-6 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6- (ethylamino) -2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- ( methylamino) -2-nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 6- (ethylamino) -3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 1,2,3,4- Tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red 14).

Suitable yellow nitro dyes are in particular: 1,2-diamino-4-nitrobenzene (CI 76.020), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2-hydroxyethoxy) -2- [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4 - [(2,3- Dihydroxypropyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 6), 2- [di (2-hydroxyethyl) amino] -5-nitrophenol, 2 - [(2-hydroxyethyl) amino] -1- methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 2-amino-4-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy) -3-methylamino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow 9), 1-chloro-2,4- bis [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 11), 1 - [(2'-ureidoethyl) amino] 4-nitrobenzene, 1-amino-4 - [(2-aminoethyl) amino] -5-methyl-2-nitrobenzene, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chloro -4 - [(2-h ydroxyethyl) amino] -3-nitrobenzene (HC Yellow 12), 4 - [(2-hydroxyethyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 13), 4 - [(2-hydroxyethyl) amino ] -3-nitrobenzonitrile (HC Yellow 14), 4 - [(2-hydroxyethyl) amino] -3-nitrobenzamide (HC Yellow 15) 3 - [(2-hydroxyethyl) amino] -4-methyl-1 -nitrobenzene, 4-chloro-3 - [(2-hydroxyethyl) amino] -1-nitrobenzene.

Suitable quinone dyes are in particular: 1,4-di [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone, 1,4-di [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 61,545, Disperse Blue 23), 1 - [(2-hydroxyethylamino] -4-methylamino-9,10-anthraquinone (CI 61.505, Disperse Blue 3), 2 - [(2-aminoethyl) amino] -9,10-anthraquinone (HC Orange 5), 1-amino-4-hydroxy-9,10-anthraquinone (CI 60.710, Disperse Red 15), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone , 7-Beta-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracenecarboxylic acid (CI 75,470, Natural Red 4), 1- [ (3-aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red 8), 1.4- Diamino-2-methoxy-9,10-anthraquinone (CI 62.015, Disperse Red 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis [(2-hydroxyethyl) amino] -9,10- anthraquinone (CI 62,500, Disperse Blue 7, Solvent Blue No. 69), 1,4-diamino-9,10-anthraquinone (CI 61.100, Disperse Violet 1), 1-amino-4 - (methylamino) -9,10-anthraquinone (C.I. 61,105, Disperse Violet 4, Solvent Violet No. 12), 2-hydroxy-3-methoxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-hydroxy-3-methyl-1,4-naphthoquinone, N- {6 - [( 3-chloro-4- (methylamino) phenyl) imino] -4-methyl-3-oxo-1,4-cyclohexadien-1-yl} urea (HC Red 9), 2 - {{4- [di (2- hydroxyethyl) amino] phenyl} amino} -5 - [(2-hydroxyethyl) amino] -2,5-cyclohexadiene-1,4-dione (HC Green 1), 5-hydroxy-1,4-naphthoquinone (CI 75,500, Natural Brown 7), 2-hydroxy-1,4-naphthoquinone (CI 75,480, Natural Orange 6), 1,2-dihydro-2- (1,3-dihydro-3-oxo-2H-indol-2-ylidene) 3H-indol-3-one (CI 73,000), 4 - {{5 - [(2-hydroxyethyl) amino] -1-methyl-1H-pyrazol-4-yl} imino} -4,5-dihydro-5 - [(2-hydroxyethyl) -imino] -1-methyl-1H-pyrazole sulfate (1: 1), hydrate (1: 1).

Particularly suitable neutral azo dyes are: 1- [di (2-hydroxyethylamino) -3-methyl-4 - [(4-nitrophenyl) azo] benzene (CI 11.210, Disperse Red 17), 1- [di (2-hydroxyethyl) amino] -4 - [(4-nitrophenyl) azo] benzene (Disperse Black 9), 4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3-methylbenzene (HC Yellow 7), 2,6-diamino-3 - [(pyridin-3-yl) azo] pyridine, 2 - {[4- (acetylamino) phenyl] azo} -4-methylphenol (CI 11855, Disperse Yellow 3), 4 - [(4-Nitrophenyl) azo] -aniline (CI 11.005, Disperse Orange 3).

Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- Chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 6-nitro-1 , 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro 6-ethylamino-4-nitrophenol.

It is not necessary that the substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing or for other reasons, eg. As toxicological, must be excluded.

Furthermore, as direct dyes also naturally occurring dyes may be used, as for example in henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

As coloring compounds of the precursors of nature-analogous dyes such indoles and indolines are preferably used, which have at least two groups selected from hydroxyl and / or or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a further embodiment, the colorants contain at least one indole and / or indoline derivative. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (RN1),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,

and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid.

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (RN2),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,
• - As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid.

Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.

The indoline or the indole derivatives can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides are used.

• (A): Kosmetisches Mittel zum Färben keratinhaltiger Fasern, insbesondere menschliche Haare, enthaltend in einem kosmetisch akzeptablen, wasserhaltigen Träger (a) mindestens eine wasserlösliche, Polyether modifizierte Verbindung der allgemeinen Formel (PE-1) [Q](K'-A-K-T)_n (PE-1) worin A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A, K und K' stehen unabhängig voneinander für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen, T steht für einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, Q ein organisches Strukturfragment, abgeleitet von linearen, verzweigten, zyklischen oder heterozyklischen Kohlenwasserstoffen, wobei all diese jeweils gesättigt, ungesättigt oder aromatisch sein dürfen, n steht für eine ganze Zahl von 3 bis 64 (insbesondere für 3, 4, 5, 6, 7 oder 8) und
• (b) mindestens ein polares Alkoxysilan der Formel (SI-1)
  
  worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, n für 1, 2 oder 3 steht, X für ein Sauerstoffatom oder eine Gruppe NH steht, R² für eine Gruppe *-(CH₂)_m-N⁺R³R⁴R⁵ steht, worin m steht für 2, 3, 4, 5 oder 6, R³, R⁴ und R⁵ unabhängig voneinander stehen für (C₁ bis C₂₀)-Alkyl, (C₈ bis C₂₀)-Acyloxy-(C₂ bis C₃)-alkyl, (C₂ bis C₂₀)-Alkenyl, (C₈ bis C₂₀)-Alkanamido-(C₂ bis C₃)-alkyl oder Aryl-(C₁ bis C₄)-alkyl, und
• (c) mindestens eine farbgebende Verbindung.
• (B): Kosmetisches Mittel zum Färben keratinhaltiger Fasern, insbesondere menschliche Haare, enthaltend in einem kosmetisch akzeptablen, wasserhaltigen Träger jeweils bezogen auf das Gewicht des Mittels (a) 0,01 bis 15,0 Gew.-%, besonders bevorzugt von 0,1 bis 8,0 Gew.-%, ganz besonders bevorzugt 0,2 bis 5,0 Gew.-%, am bevorzugtesten von 0,25 bis 2,5 Gew.-%, mindestens einer wasserlöslichen, Polyether modifizierten Verbindung der allgemeinen Formel (PE-1) [Q](K'-A-K-T)_n (PE-1) worin A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A, K und K' stehen unabhängig voneinander für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen, T steht für einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, Q ein organisches Strukturfragment, abgeleitet von linearen, verzweigten, zyklischen oder heterozyklischen Kohlenwasserstoffen, wobei all diese jeweils gesättigt, ungesättigt oder aromatisch sein dürfen, n steht für eine ganze Zahl von 3 bis 64 (insbesondere für 3, 4, 5, 6, 7 oder 8) und (b) 0,01 bis 15,0 Gew.-%, besonders bevorzugt von 0,1 bis 8,0 Gew.-%, ganz besonders bevorzugt 0,2 bis 5,0 Gew.-%, am bevorzugtesten von 0,25 bis 2,5 Gew.-%, mindestens eines polaren Alkoxysilans der Formel (SI-1)
  
  worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, n für 1, 2 oder 3 steht, X für ein Sauerstoffatom oder eine Gruppe NH steht, R² für eine Gruppe *-(CH₂)_m-N⁺R³R⁴R⁵ steht, worin m steht für 2, 3, 4, 5 oder 6, R³, R⁴ und R⁵ unabhängig voneinander stehen für (C₁ bis C₂₀)-Alkyl, (C₈ bis C₂₀)-Acyloxy-(C₂ bis C₃)-alkyl, (C₂ bis C₂₀)-Alkenyl, (C₈ bis C₂₀)-Alkanamido-(C₂ bis C₃)-alkyl oder Aryl-(C₁ bis C₄)-alkyl, und (c) mindestens eine farbgebende Verbindung.
• (C): Kosmetisches Mittel zum Färben keratinhaltiger Fasern, insbesondere menschliche Haare, enthaltend in einem kosmetisch akzeptablen, wasserhaltigen Träger (a) mindestens eine wasserlösliche, Polyether modifizierte Verbindung der allgemeinen Formel (PE-1) [Q](K'-A-K-T)_n (PE-1) worin A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A, K und K' stehen unabhängig voneinander für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen, T steht für einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, Q ein organisches Strukturfragment, abgeleitet von Glyzerin, Monosaccharid oder Disaccharid, n steht für eine ganze Zahl von 3 bis 64 (insbesondere für 3, 4, 5, 6, 7 oder 8) und (b) mindestens ein polares Alkoxysilan der Formel (SI)
  
  worin G für eine (C₁ bis C₃)-Alkylengruppe steht, K'' für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen steht, R¹ für ein Molekülfragment steht, umfassend mindestens einen polaren Substituenten ausgewählt aus mindestens einem Vertreter aus der Gruppe, die gebildet wird aus quaternisierten Stickstoffatomen Aminogruppen anionischen Resten x für 1, 2 oder 3 steht, R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, und (c) mindestens eine farbgebende Verbindung.
• (D): Kosmetisches Mittel zum Färben keratinhaltiger Fasern, insbesondere menschliche Haare, enthaltend in einem kosmetisch akzeptablen, wasserhaltigen Träger (a) mindestens eine wasserlösliche, Polyether modifizierte Verbindung der allgemeinen Formel (PE-1) [Q](K'-A-K-T)_n (PE-1) worin A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A, K und K' stehen unabhängig voneinander für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen, T steht für einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, Q ein organisches Strukturfragment, abgeleitet von Glyzerin, Monosaccharid oder Disaccharid, n steht für eine ganze Zahl von 3 bis 64 (insbesondere für 3, 4, 5, 6, 7 oder 8) und (b) mindestens ein polares Alkoxysilan der Formel (SI-1)
  
  worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, n für 1, 2 oder 3 steht, X für ein Sauerstoffatom oder eine Gruppe NH steht, R² für eine Gruppe *-(CH₂)_m-N⁺R³R⁴R⁵ steht, worin m steht für 2, 3, 4, 5 oder 6, R³, R⁴ und R⁵ unabhängig voneinander stehen für (C₁ bis C₂₀)-Alkyl, (C₈ bis C₂₀)-Acyloxy-(C₂ bis C₃)-alkyl, (C₂ bis C₂₀)-Alkenyl, (C₈ bis C₂₀)-Alkanamido-(C₂ bis C₃)-alkyl oder Aryl-(C₁ bis C₄)-alkyl, und (c) mindestens eine farbgebende Verbindung.
• (E): Kosmetisches Mittel zum Färben keratinhaltiger Fasern, insbesondere menschliche Haare, enthaltend in einem kosmetisch akzeptablen, wasserhaltigen Träger jeweils bezogen auf das Gewicht des Mittels (a) 0,01 bis 15,0 Gew.-%, besonders bevorzugt von 0,1 bis 8,0 Gew.-%, ganz besonders bevorzugt 0,2 bis 5,0 Gew.-%, am bevorzugtesten von 0,25 bis 2,5 Gew.-%, mindestens einer wasserlöslichen, Polyether modifizierten Verbindung der allgemeinen Formel (PE-1) [Q][K'-A-K-T)_n (PE-1) worin A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A, K und K' stehen unabhängig voneinander für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen, T steht für einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, Q ein organisches Strukturfragment, abgeleitet von Glyzerin, Monosaccharid oder Disaccharid, n steht für eine ganze Zahl von 3 bis 64 (insbesondere für 3, 4, 5, 6, 7 oder 8) und (b) 0,01 bis 15,0 Gew.-%, besonders bevorzugt von 0,1 bis 8,0 Gew.-%, ganz besonders bevorzugt 0,2 bis 5,0 Gew.-%, am bevorzugtesten von 0,25 bis 2,5 Gew.-%, mindestens eines polaren Alkoxysilans der Formel (SI-1)
  
  worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, n für 1, 2 oder 3 steht, X für ein Sauerstoffatom oder eine Gruppe NH steht, R² für eine Gruppe *-(CH₂)_m-N⁺R³R⁴R⁵ steht, worin m steht für 2, 3, 4, 5 oder 6, R³, R⁴ und R⁵ unabhängig voneinander stehen für (C₁ bis C₂₀)-Alkyl, (C₈ bis C₂₀)-Acyloxy-(C₂ bis C₃)-alkyl, (C₂ bis C₂₀)-Alkenyl, (C₈ bis C₂₀)-Alkanamido-(C₂ bis C₃)-alkyl oder Aryl-(C₁ bis C₄)-alkyl, und (c) mindestens eine farbgebende Verbindung.
• (F): Kosmetisches Mittel zum Färben keratinhaltiger Fasern, insbesondere menschliche Haare, enthaltend in einem kosmetisch akzeptablen, wasserhaltigen Träger jeweils bezogen auf das Gewicht des Mittels (a) 0,01 bis 15,0 Gew.-%, besonders bevorzugt von 0,1 bis 8,0 Gew.-%, ganz besonders bevorzugt 0,2 bis 5,0 Gew.-%, am bevorzugtesten von 0,25 bis 2,5 Gew.-%, mindestens einer wasserlöslichen, Polyether modifizierten Verbindung der allgemeinen Formel (PE-1) [Q](K'-A-K-T)_n (PE-1) worin A eine Polyoxyalkylenkette aus Ethylenoxideinheiten oder aus Ethylenoxid- und Propylenoxid-Einheiten bedeutet, mit einem maximalen Anteil von 50 Gew.-% an Propylenoxid-Einheiten, bezogen auf das Gewicht von A, K und K' stehen unabhängig voneinander für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen, T steht für einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, Q ein organisches Strukturfragment, abgeleitet von Glyzerin, Monosaccharid oder Disaccharid, n steht für eine ganze Zahl von 3 bis 64 (insbesondere für 3, 4, 5, 6, 7 oder 8) und (b) 0,01 bis 15,0 Gew.-%, besonders bevorzugt von 0,1 bis 8,0 Gew.-%, ganz besonders bevorzugt 0,2 bis 5,0 Gew.-%, am bevorzugtesten von 0,25 bis 2,5 Gew.-%, mindestens eines polaren Alkoxysilans der Formel (SI)
  
  worin G für eine (C₁ bis C₃)-Alkylengruppe steht, K'' für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen steht, R¹ für ein Molekülfragment steht, umfassend mindestens einen polaren Substituenten ausgewählt aus mindestens einem Vertreter der Gruppe, die gebildet wird aus quaternisierten Stickstoffatomen Aminogruppen anionischen Resten x für 1, 2 oder 3 steht, R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen steht, und (c) mindestens eine farbgebende Verbindung.

Very particularly preferred cosmetic agents according to the invention obey at least one of the following embodiments (A) to (F):

• (A): Cosmetic agent for dyeing keratin-containing fibers, in particular human hair, comprising, in a cosmetically acceptable, water-containing carrier (a) at least one water-soluble, polyether-modified compound of the general formula (PE-1) [Q ] ( K'-AKT) _n (PE-1) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A, K and K 'are independently selected for connectivity from a covalent bond or from a molecular fragment with two free valencies, T is a radical * -Si (OR) _x (R ') _3-x , wherein R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1, 2 or 3, Q is an organic structural fragment derived from linear, branched, cyclic or heterocyclic Hydrocarbons, all of which may be saturated, unsaturated or aromatic, n is an integer from 3 to 64 (in particular 3, 4, 5, 6, 7 or 8) and
• (b) at least one polar alkoxysilane of the formula (SI-1)
  
  wherein R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1, 2 or 3, n is 1, 2 or 3, X is an oxygen atom or a group NH, R ^{2 is} a group * - (CH ₂ ) _m -N ⁺ R ³ R ⁴ R ⁵ , wherein m is 2, 3, 4, 5 or 6, R ³ , R ⁴ and R ⁵ independently of one another are (C ₁ to C ₂₀ ) -alkyl, (C ₈ to C ₂₀ ) -acyloxy- (C ₂ to C ₃ ) -alkyl, (C ₂ to C ₂₀ ) -alkenyl, (C ₈ to C ₂₀ ) -Alkanamido (C ₂ to C ₃ ) -alkyl or aryl- (C ₁ to C ₄ ) -alkyl, and
• (c) at least one coloring compound.
• (B): Cosmetic agent for dyeing keratin-containing fibers, in particular human hair, contained in a cosmetically acceptable, water-containing carrier in each case based on the weight of the agent (a) 0.01 to 15.0 wt .-%, particularly preferably of 0, From 1 to 8.0 wt%, most preferably from 0.2 to 5.0 wt%, most preferably from 0.25 to 2.5 wt%, of at least one water-soluble, polyether-modified compound of the general formula (PE-1) [Q ] ( K'-AKT) _n (PE-1) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A, K and K 'are independently selected for connectivity from a covalent bond or from a molecular fragment with two free valencies, T is a radical * -Si (OR) _x (R ') _3-x , wherein R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1, 2 or 3, Q is an organic structural fragment derived from linear, branched, cyclic or heterocyclic Hydrocarbons, all of which may be saturated, unsaturated or aromatic, n is an integer from 3 to 64 (especially for 3, 4, 5, 6, 7 or 8) and (b) 0.01 to 15.0 Wt .-%, particularly preferably from 0.1 to 8.0 wt .-%, most preferably 0.2 to 5.0 wt .-%, most preferably from 0.25 to 2.5 wt .-%, at least one polar alkoxysilane of the formula (SI-1)
  
  wherein R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1, 2 or 3, n is 1, 2 or 3, X is an oxygen atom or a group NH stands, R ^{2 is} a group * - (CH ₂ ) _m -N ⁺ R ³ R ⁴ R ⁵ , where m is 2, 3, 4, 5 or 6, R ³ , R ⁴ and R ⁵ are each independently ( C ₁ to C ₂₀ ) -alkyl, (C ₈ to C ₂₀ ) -acyloxy- (C ₂ to C ₃ ) -alkyl, (C ₂ to C ₂₀ ) -alkenyl, (C ₈ to C ₂₀ ) -alkanamido ( C ₂ to C ₃ ) alkyl or aryl (C ₁ to C ₄ ) alkyl, and (c) at least one coloring compound.
• (C): Cosmetic agent for dyeing keratin-containing fibers, in particular human hair, comprising, in a cosmetically acceptable, water-containing carrier (a) at least one water-soluble, polyether-modified compound of the general formula (PE-1) [Q ] ( K'-AKT) _n (PE-1) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50 wt .-% of propylene oxide units, based on the weight of A, K and K 'independently stand for a connectivity selected from a covalent bond or a molecular fragment with two free valences, T is a radical * -Si (OR) _x (R ') _3-x , wherein R and R 'independently of one another represent a (C ₁ to C ₄ ) alkyl group (especially methyl or ethyl), x is 1, 2 or 3, Q is an organic structural fragment derived from glycerol, monosaccharide or disaccharide, n is an integer from 3 to 64 (in particular 3, 4, 5, 6, 7 or 8) and (b) at least one polar alkoxysilane of the formula (SI)
  
  wherein G is a (C ₁ to C ₃ ) alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized nitrogen atoms, amino groups of anionic radicals x is 1, 2 or 3, R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) and (c) at least one coloring compound.
• (D): Cosmetic agent for dyeing keratin-containing fibers, in particular human hair, comprising, in a cosmetically acceptable, water-containing carrier (a) at least one water-soluble, polyether-modified compound of the general formula (PE-1) [Q ] ( K'-AKT) _n (PE-1) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A, K and K 'are independently selected for connectivity from a covalent bond or from a molecular fragment with two free valencies, T is a radical * -Si (OR) _x (R ') _3-x , wherein R and R 'independently of one another represent a (C ₁ to C ₄ ) alkyl group (especially methyl or ethyl), x is 1, 2 or 3, Q is an organic structural fragment derived from glycerol, monosaccharide or disaccharide, n is an integer from 3 to 64 (in particular 3, 4, 5, 6, 7 or 8) and (b) at least one polar alkoxysilane of the formula (SI-1)
  
  wherein R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1, 2 or 3, n is 1, 2 or 3, X is an oxygen atom or a group NH, R ^{2 is} a group * - (CH ₂ ) _m -N ⁺ R ³ R ⁴ R ⁵ , wherein m is 2, 3, 4, 5 or 6, R ³ , R ⁴ and R ⁵ independently of one another are (C ₁ to C ₂₀ ) -alkyl, (C ₈ to C ₂₀ ) -acyloxy- (C ₂ to C ₃ ) -alkyl, (C ₂ to C ₂₀ ) -alkenyl, (C ₈ to C ₂₀ ) Alkanamido (C ₂ to C ₃ ) alkyl or aryl (C ₁ to C ₄ ) alkyl, and (c) at least one coloring compound.
• (E): Cosmetic agent for dyeing keratin-containing fibers, in particular human hair, containing in a cosmetically acceptable, water-containing carrier in each case based on the weight of the agent (a) from 0.01 to 15.0% by weight, particularly preferably from 0, From 1 to 8.0 wt%, most preferably from 0.2 to 5.0 wt%, most preferably from 0.25 to 2.5 wt%, of at least one water-soluble, polyether-modified compound of the general formula (PE-1) [Q ] [ K'-AKT) _n (PE-1) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A, K and K 'are independently selected for connectivity from a covalent bond or from a molecular fragment with two free valencies, T is a radical * -Si (OR) _x (R ') _3-x , wherein R and R 'independently of one another represent a (C ₁ to C ₄ ) alkyl group (especially methyl or ethyl), x is 1, 2 or 3, Q is an organic structural fragment derived from glycerol, monosaccharide or disaccharide, n is an integer from 3 to 64 (especially for 3, 4, 5, 6, 7 or 8) and (b) 0.01 to 15.0 wt .-%, particularly preferably from 0.1 to 8.0 % By weight, most preferably from 0.2 to 5.0% by weight, most preferably from 0.25 to 2.5% by weight, of at least one polar alkoxysilane of formula (SI-1)
  
  wherein R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1, 2 or 3, n is 1, 2 or 3, X is an oxygen atom or a group NH, R ^{2 is} a group * - (CH ₂ ) _m -N ⁺ R ³ R ⁴ R ⁵ , wherein m is 2, 3, 4, 5 or 6, R ³ , R ⁴ and R ⁵ independently of one another are (C ₁ to C ₂₀ ) -alkyl, (C ₈ to C ₂₀ ) -acyloxy- (C ₂ to C ₃ ) -alkyl, (C ₂ to C ₂₀ ) -alkenyl, (C ₈ to C ₂₀ ) Alkanamido (C ₂ to C ₃ ) alkyl or aryl (C ₁ to C ₄ ) alkyl, and (c) at least one coloring compound.
• (F): Cosmetic agent for dyeing keratin-containing fibers, in particular human hair, containing in a cosmetically acceptable, water-containing carrier in each case based on the weight of the agent (a) 0.01 to 15.0 wt .-%, particularly preferably of 0, From 1 to 8.0 wt%, most preferably from 0.2 to 5.0 wt%, most preferably from 0.25 to 2.5 wt%, of at least one water-soluble, polyether-modified compound of the general formula (PE-1) [Q ] ( K'-AKT) _n (PE-1) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A, K and K 'are independently selected for connectivity from a covalent bond or from a molecular fragment with two free valencies, T is a radical * -Si (OR) _x (R ') _3-x , wherein R and R 'independently of one another represent a (C ₁ to C ₄ ) alkyl group (especially methyl or ethyl), x is 1, 2 or 3, Q is an organic structural fragment derived from glycerol, monosaccharide or disaccharide, n is an integer from 3 to 64 (especially for 3, 4, 5, 6, 7 or 8) and (b) 0.01 to 15.0 wt .-%, particularly preferably from 0.1 to 8.0 % By weight, most preferably from 0.2 to 5.0% by weight, most preferably from 0.25 to 2.5% by weight, of at least one polar alkoxysilane of the formula (SI)
  
  wherein G is a (C ₁ to C ₃ ) alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized nitrogen atoms, amino groups of anionic radicals x is 1, 2 or 3, R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl) and (c) at least one coloring compound.

The embodiments (A) to (F) of the cosmetic agent according to the invention preferably contain as coloring compound preferably at least one oxidation dye precursor of the developer component type and optionally additionally at least one coupler component. In the context of embodiments A) to (F), of course, mutatis mutandis apply the respective marked preferred features of components (a) and (b) of the active ingredient combination, in particular the previously mentioned as preferred ratios of components (a) and (b).

• (a) mindestens ein wasserlösliches Polymer umfassend mindestens einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, und
• (b) mindestens eine polare Alkoxysilanverbindung der Formel (SI)
  
  worin G für eine (C₁ bis C₃)-Alkylengruppe steht, K'' für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen steht, R¹ für ein Molekülfragment steht, umfassend mindestens einen polaren Substituenten ausgewählt aus mindestens einem Vertreter aus der Gruppe, die gebildet wird aus quaternisierten Stickstoffatomen Aminogruppen anionischen Resten x für 1, 2 oder 3 steht, R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, und
• (c) mindestens Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusätzlich mindestens eine Kupplerkomponente als farbgebende Verbindung, und
• (d) mindestens ein Oxidationsmittel.

The active ingredient combination used according to the invention has its effect especially in agents for the oxidative dyeing of keratin-containing fibers, in particular human hair. It has therefore been found preferable to use an inventive agent for the oxidative dyeing of keratin-containing fibers, comprising in a cosmetic carrier

• (A) at least one water-soluble polymer comprising at least one radical * -Si (OR) _x (R ') _3-x , wherein R and R' independently of one another for a (C ₁ to C ₄ ) alkyl group (in particular methyl or ethyl ), x is 1, 2 or 3, and
• (b) at least one polar alkoxysilane compound of the formula (SI)
  
  wherein G is a (C ₁ to C ₃ ) -alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized nitrogen atoms of amino groups anionic radicals x is 1, 2 or 3, R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl), and
• (c) at least one oxidation dye precursor of the developer component type and optionally additionally at least one coupler component as the coloring compound, and
• (d) at least one oxidizing agent.

For (a) and (b) and (c), the aforementioned preferred features (vide supra) apply.

• – mindestens ein Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusätzlich mindestens eine Kupplerkomponente und
• – mindestens ein Oxidatiosmittel zuzusetzen.

It is particularly preferred according to the invention, the inventive agents (A) to (F) additionally

• At least one oxidation dye precursor of the developer component type and optionally additionally at least one coupler component and
• - Add at least one oxidant.

The oxidizing agents according to the invention are different from atmospheric oxygen and have such an oxidation potential that makes it possible to oxidize a developer-type oxidation dye precursor. The oxidizing agent is preferably hydrogen peroxide and / or at least one addition product thereof, in particular to inorganic or organic compounds such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone · n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and Melamine peroxide, in question.

The oxidizing agent is preferably contained in an amount of from 1.0 to 10% by weight, in particular from 3.0 to 10.0% by weight, in each case based on the weight of the ready-to-use cosmetic colorant, in the cosmetic composition.

In a preferred embodiment of the invention, the cosmetic colorant according to the invention prior to application of a first composition containing in a cosmetic carrier at least one color-changing component, and a second composition containing in a cosmetic carrier at least one oxidizing agent, with the proviso that the first composition and / or the second composition contains at least one active substance combination of the first subject of the invention. The first and second compositions are packaged separately in each case in a compartment and provided together in a packaging unit (kit). Shortly before use, both components are mixed together. The resulting ready-to-use dye preparation preferably has a pH in the range from 6 to 12, in particular from pH 7.5 to 10, on.

The cosmetic colorant according to the invention preferably contains at least one alkalizing agent. The alkalizing agents usable in the invention and are preferably selected from at least one member of the group formed from ammonia, basic amino acids, alkali hydroxides, alkanolamines, alkali metal metasilicates, urea, alkali phosphates and alkali hydrogen phosphates. The alkali metal ions used are preferably lithium, sodium, potassium, in particular sodium or potassium. Again, preferably, the alkalizing agents are different from ammonia. The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group formed from L-arginine, D-arginine, D, L-arginine, L-histidine, D-histidine, D, L-histidine, L-lysine, D-lysine, D, L-lysine, more preferably L-arginine, D-arginine, D, L-arginine used as an alkalizing agent according to the invention. The alkali metal hydroxides which can be used as the alkalizing agent according to the invention are preferably selected from the group formed from sodium hydroxide and potassium hydroxide. The alkanolamines which can be used as alkalizing agents according to the invention are preferably selected from primary amines having a C ₂ -C ₅ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1 -Aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol , 1-amino-2-methylpropan-2-ol, 3 Aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol. Very particularly preferred alkanolamines according to the invention are selected from the group consisting of 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropane-1,3-diol.

The alkalizing agent is particularly preferably selected from at least one compound from the group formed from 2-aminoethanol, 2-amino-2-methylpropan-1-ol, 2-amino-2-methylpropane-1,3-diol, Potassium hydroxide, L-arginine, D-arginine, DL-arginine, N-methylglucamine and urea.

Furthermore, the colorants of the invention, other active ingredients, auxiliaries and additives, such as nonionic polymers; cationic polymers; zwitterionic and amphoteric polymers; anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers, and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers ; hair conditioning compounds such as phospholipids; Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates; Perfume oils, dimethylisosorbide and cyclodextrins; fiber structure improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose; cationic surfactants; defoamers; Anti-dandruff agents; Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines; Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol; Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H; Plant extracts, in particular extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng or ginger root; Cholesterol; Bodying agents; Fats and waxes; complexing; Swelling and penetrating substances; Opacifiers; pearlescent agents; solid-shaped pigments; Stabilizing agents for hydrogen peroxide and other oxidizing agents; Propellant; antioxidants; contain.

The preferred embodiments of the first subject of the invention apply to the second subject of the invention mutatis mutandis.

• (a) mindestens einem wasserlöslichen Polymer umfassend mindestens einen Rest *-Si(OR)_x(R')_3-x, worin R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen, x für 1, 2 oder 3 steht, und
• (b) mindestens einer polaren Alkoxysilanverbindung der Formel (SI)
  
  worin G für eine (C₁ bis C₃)-Alkylengruppe steht, K'' für eine Konnektivität, ausgewählt aus einer kovalenten Bindung oder aus einem Molekülfragment mit zwei freien Valenzen steht, R¹ für ein Molekülfragment steht, umfassend mindestens einen polaren Substituenten ausgewählt aus mindestens einem Vertreter aus der Gruppe, die gebildet wird aus quaternisierten Stickstoffatomen Aminogruppen anionischen Resten x für 1, 2 oder 3 steht, R und R' unabhängig voneinander für eine (C₁ bis C₄)-Alkylgruppe (insbesondere für Methyl oder Ethyl) stehen,

auf mit mindestens einer farbgebenden Verbindung künstlich gefärbte keratinhaltige Fasern (insbesondere menschlichen Haaren) einwirkt und nach einer Einwirkungszeit wieder abgespült wird. Eine bevorzugte Ausführungsform dieses erfindungsgemäßen Verfahrens ist ein Verfahren zur Färbung keratinhaltiger Fasern, bei dem ein Mittel des zweiten Erfindungsgegenstandes auf die Fasern aufgetragen wird und nach einer Einwirkungszeit wieder abgespült wird.A third object of the present invention is a cosmetic process in which a combination of active ingredients

• (A) at least one water-soluble polymer comprising at least one radical * -Si (OR) _x (R ') _3-x , wherein R and R' independently of one another for a (C ₁ to C ₄ ) alkyl group (in particular methyl or ethyl ), x is 1, 2 or 3, and
• (b) at least one polar alkoxysilane compound of the formula (SI)
  
  wherein G is a (C ₁ to C ₃ ) alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized nitrogen atoms, amino groups of anionic radicals x is 1, 2 or 3, R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) stand,

act on artificially colored keratin fibers (in particular human hair) with at least one coloring compound and rinsed again after an exposure time. A preferred embodiment of this process according to the invention is a process for dyeing keratin-containing fibers an agent of the second subject of the invention is applied to the fibers and rinsed again after an exposure time.

The application temperatures can range between 15 and 40 ° C. After a contact time of usually 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is eliminated if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

The preferred embodiments of the first and second subject of the invention apply mutatis mutandis to the third subject of the invention.

Examples

The molecular weights given in the examples are number-average molecular weights of the starting compounds (polyether polyols) which were used to prepare the prepolymers. The number average molecular weight of the polyols can be calculated by end group determination on the basis of the knowledge of the functionality of the compounds or the functionality of the mixture components and the OH number of the compound or mixture (determined by DIN 53240 ). In the event that other compounds are used as starting compounds instead of the polyols, their number-average molecular weight is decisive. Thus, for example, the number-average molecular weight of amines can be determined by end-group determination by potentiometric titration after DIN 16945 be determined.

Preparation of suitable water-soluble polymers:

Example 1: Three-armed triethoxysilyl-terminated polyether (PP1):

The polyether polyol used is a 3-arm random poly (ethylene oxide-co-propylene oxide) based on glycerol (see the above formula (PE-1f)) having an EO / PO ratio of 80/20 and a number average molecular weight of about 5000 g / mol, obtained from Dow Chemicals (Voranol CP ^® 1421). Before the reaction, the polyol was heated in vacuo with stirring for 1 h at 80 ° C. To the dried polyether polyol (2.04 g, 0.41 mmol) was added slowly (3-isocyanatopropyl) triethoxysilane (317 mg, 1.0 eq.). The reaction mixture was further stirred under inert gas at 100 ° C for 2 days until the vibration band of the NCO group disappeared by an IR measurement. A product is obtained in which a triethoxysilyl group is in each case present at the free ends of the polymer arms of the star-shaped prepolymer. The product is a colorless, viscous liquid.

2.0 staining

• – SIa = 3-Aminopropyltriethoxysilan
• – SIb = Silan der Formel (SI-1c) (R steht für eine lineare C₁₆-Acylgruppe und R³ für Methyl) eingearbeitet. Die resultierende modifizierte Färbecreme wurde ummittelbar vor der Applikation auf Haarsträhnen (1 g standardisiertes Haar „European natural hair 6/0” Charge # 06/2010, N93 der Firma Kerling International, Deutschland, an einem Ende zum Haarbündel verklebt) mit einer handelsüblichen 6 Gew.-% Wasserstoffperoxid-haltigen Entwicklerdispersion Oxigenta (Schwarzkopf) im Gewichtsverhältnis 1 zu 1 zu einem erfindungsgemäßen Haarfärbemittel gemischt.

The dyeing cream of the commercial product Igors Royal 6-88 (Schwarzkopf) was based on the total weight of the mixture 0.5 wt .-% of a water-soluble polymer PP1 in combination with 0.5 wt .-% of a polar alkoxysilane

• - SIa = 3-aminopropyltriethoxysilane
• - SIb = silane of the formula (SI-1c) (R is a linear C ₁₆ acyl group and R ^{3 is} methyl) incorporated. The resulting modified staining cream was immediately before application to hair tresses (1 g of standardized hair "European natural hair 6/0" Lot # 06/2010, N93 Kerling International, Germany, glued at one end to the hair bundle) with a commercial 6 wt .-% hydrogen peroxide developer dispersion Oxigenta (Schwarzkopf) in a weight ratio of 1 to 1 mixed to a hair dye according to the invention.

The ready-to-use colorant was then applied to a hair strand in a weight ratio of 4 g of colorant to 1 g of hair, allowed to act for 30 minutes at 32 ° C and rinsed by the fiber. A total of 4 strands of hair were dyed with it. In addition, 4 strands of hair were dyed according to the above procedure with the above commercial product without addition of the said tapioca starch (not according to the invention).

The tresses were each allowed to dry and measured colorimetrically by determining the L, a, b starting values per tress (device Spectraflash 450, software color tools). Per hair strand 8 measuring points were taken and for each value of the invention colored streaks in one group and the non-inventive colored streaks in another group, the respective arithmetic mean of the Group to obtain the respective values L ₀ , a ₀ , b ₀ determined. The same procedure was followed in the following colorimetric measurements.

To determine the wash fastness, the hair strands were subjected to a washing procedure that simulates hair washing:
An ultrasonic bath was filled with aqueous shampoo solution (2% by weight foam shampoo "7 herbs"). The colored hair strands were immersed in this washing solution and treated with ultrasound (step 5) for 15 minutes. This treatment corresponds to the cleaning performance of six washes. The tresses were then rinsed thoroughly, dried and measured again by colorimetry. The tresses were then subjected to another wash cycle. The washfastness rating was calculated by calculating the color difference of the tresses before washing and after each washing cycle and is calculated as follows: ΔE = [(L _i -L ₀ ) ² + (a _i -a ₀ ) ² + (b _i -b ₀ ) ² ] ^1/2 L _i, a _i, b _i Values after 6, 12, 18, 24 and 36 washes L ₀ , a ₀ , b ₀ Values after 0 hair washes hair strand Table 1: ΔE after 6, 12, 18, 24 and 30 washes Number of washes 6 12 18 24 30 commercial product 2.8 3.4 4.8 5.9 7.1 invention Agent with PP1 / SIa 2.1 3.3 3.9 4.6 5.8 invention invention Agent with PP1 / SIb 2.1 3.0 3.6 3.9 4.5

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2009/024450 A1 [0009]
• WO 2011/015512 A1 [0010]
• WO 2011/015513 A1 [0010]
• WO 2011/015514 A1 [0010]
• EP 998908 A2 [0168]

Cited non-patent literature

• DIN 53240 [0204]
• DIN 16945 [0204]

Claims (15)

Use of a combination of active ingredients of (a) at least one water-soluble polymer comprising at least one radical in which R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl), x is 1, 2 or 3 and (b) at least one polar alkoxysilane compound of the formula (SI)

wherein G is a (C ₁ to C ₃ ) alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized nitrogen atoms, amino groups of anionic radicals x is 1, 2 or 3, R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) to improve artificial colouration of coloring compounds on keratin-containing fibers, in particular human hair, Cosmetic agent for coloring keratin-containing fibers, in particular human hair, containing in a cosmetic carrier (a) at least one water-soluble polymer comprising at least one radical * -Si (OR) _x (R ') _3-x , where R and R' independently of one another a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1, 2 or 3, and (b) at least one polar alkoxysilane compound of the formula (SI)

wherein G is a (C ₁ to C ₃ ) alkylene group, K '' is a connectivity selected from a covalent bond or a molecular fragment having two free valencies, R ^{1 is} a molecular fragment comprising at least one polar substituent selected from at least one member of the group formed from quaternized nitrogen atoms, amino groups of anionic radicals x is 1, 2 or 3, R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (in particular methyl or ethyl) and (c) at least one coloring compound. Cosmetic coloring agent according to claim 2, characterized in that said water-soluble polymer is at least one water-soluble, polyether-modified, organic polymer comprising at least one polyether structural unit, preferably at least 3 polyether structural units, said polyether structural unit comprising (i) a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, having a maximum proportion of 50% by weight of propylene oxide units, based on the weight of the polyoxyalkylene chain, and (ii) having at least one radical in which R and R 'independently of one another are C ₁ to C ₄ ) alkyl group (in particular methyl or ethyl), x is 1, 2 or 3. Cosmetic coloring agent according to one of claims 2 or 3, characterized in that said water-soluble polymer is selected from at least one compound of general formula (PE-1) [Q ] ( K'-AKT) _n (PE-1) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A, K and K 'are independently selected for connectivity from a covalent surf or from a molecular fragment with two free valencies, T is a radical * -Si (OR) _x (R ') _3-x , wherein R and R 'independently of one another represent a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1, 2 or 3, Q means an organic structural fragment derived from linear, branched, cyclic or heterocyclic hydrocarbons, all of which may be saturated, unsaturated or aromatic, n is an integer from 3 to 64 (in particular 3, 4, 5, 6, 7 or 8). Cosmetic coloring agent according to any one of claims 2 to 4, characterized in that said water-soluble polymer is selected from at least one compound of general formula (PE-2) TKA-K'-T '(PE-2) wherein A represents a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide units, with a maximum proportion of 50% by weight of propylene oxide units, based on the weight of A, K and K 'are independently selected for connectivity from a covalent bond or from a molecule fragment with two free valences, T and T stand for a molecule fragment comprising at least one radical -Si (OR) _x (R ') _3-x in which R and R' independently of one another represent a (C ₁ to C ₄ ) alkyl group (in particular methyl or ethyl), x is 1, 2 or 3. Cosmetic coloring agent according to any one of claims 2 to 5, characterized in that said water-soluble polymer is selected from solid particles (i) surface-modified with polyethers, the polyethers being a polyoxyalkylene chain of ethylene oxide units or of ethylene oxide and propylene oxide Units having a maximum proportion of 50% by weight of propylene oxide units, based on the weight of the polyoxyalkylene chain, (ii) have at least one radical * -Si (OR) _x (R ') _3-x , where R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1, 2 or 3. Cosmetic coloring agent according to one of Claims 2 to 6, characterized in that A represents a structural fragment of the formula (A1) * - (OCH ₂ CH ₂ ) _n - (OCH ₂ CH (CH ₃ )) _m - * (A1) wherein n is an integer of 1 to 500, m is an integer of 0 to 500, and the structural fragment of the formula (A1) has a maximum content of 50 wt% of propylene oxide units based on the weight of the structural fragment (A1 ) Has. Cosmetic coloring agent according to one of claims 2 to 7, characterized in that the radicals K, K 'and K "independently of one another for a covalent surf, an oxy group, an imino group, a (C ₁ to C ₆ ) alkylene group or at least one of the following Konnektivitäten (K1) to (K10) are

wherein R and R '' are independently methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3- diyl, butane-1,4-diyl or phenylene, R 'represents a hydrogen atom or a (C ₁ to C ₄ ) alkyl group, R''' independently of one another means a (C ₁ to C ₄ ) alkyl group or an aryl group. Cosmetic dyeing agent according to any one of claims 2 to 8, characterized in that the said water-soluble polymers of component (a) are present in an amount of from 0.01 to 15.0% by weight, preferably from 0.1 to 8.0 Wt .-%, particularly preferably 0.2 to 5.0 wt .-%, most preferably from 0.25 to 2.5 wt .-%, each based on the weight of the total composition, are included. Cosmetic coloring agent according to any one of Claims 2 to 9, characterized in that, as the polar alkoxysilane of the formula (SI), it comprises at least one compound of the formula (SI-1)

wherein R and R 'independently of one another are a (C ₁ to C ₄ ) -alkyl group (especially methyl or ethyl), x is 1,2 or 3, n is 1, 2 or 3, X is an oxygen atom or a group NH, R ² is a group * - (CH ₂ ) _m -NR ³ R ⁴ wherein m is 2, 3, 4, 5 or 6, R ³ and R ^{4 are} independently (C ₁ to C ₂₀ ) alkyl, (C ₈ to C ₂₀ ) acyloxy (C ₂ to C ₃ ) alkyl, (C ₂ to C ₂₀ ) alkenyl, (C ₈ to C ₂₀ ) alkanamido (C ₂ to C ₃ ) -alkyl or aryl- (C ₁ to C ₄ ) -alkyl. Cosmetic coloring agent according to one of Claims 2 to 10, characterized in that said polar alkoxysilanes of component (b) are present in an amount of from 0.01 to 15.0% by weight, preferably from 0.1 to 8.0 Wt .-%, particularly preferably 0.2 to 5.0 wt .-%, most preferably from 0.25 to 2.5 wt .-%, each based on the weight of the total composition, are included. Cosmetic coloring agent according to any one of Claims 2 to 11, characterized in that said water-soluble polymers of component (a) and the polar alkoxysilanes of component (b) are present in a weight ratio range of 10: 1 to 1: 10, preferably 4: 1 1 to 1 to 4, more preferably from 1 to 1 to 1 to 2, are included. Cosmetic coloring agent according to any one of claims 2 to 12, characterized in that it additionally contains at least one compound selected from organic amines comprising 2 to 20 carbon atoms, carboxylate complex compounds of tin, alkoxide compounds of tin, Lead carboxylate complex compounds, organoaluminum compounds, metal complexes of organic dicarbonyl compounds, metal complexes of organic dicarboxylic acid esters. Cosmetic coloring agent according to one of claims 2 to 13, characterized in that in addition at least one oxidizing agent, in particular hydrogen peroxide and / or at least one addition product thereof, is contained. Cosmetic dyeing agent according to any one of claims 2 to 14, characterized in that the coloring compound is selected from at least one oxidation dye precursor of the developer component type and optionally additionally at least one coupler component.